Slaves S Ue UN ele ine IN We oS eR 1S os} APPLIED COLLOID CHEMISTRY General Theory pecs aMPEV ime Ri aau it Osta Peaswww. forgotienbooks. org ISBN 9781440093135Rorgotten Books This is a Forgotten Books Library high-quality e-book from www.forgottenbooks.org Thank you for supporting Forgotten Books by purchasing this e-book. This e-book may not be distributed. If you wish to share this e-book with friends or other people, please give them the free low-quality version from www.forgottenbooks.org This book is also available in print as high-quality paperback from www.amazon.comVERTICAL LINES The vertical black lines appearing on most pages are deliberate. This is required to stop people from selling printed copies of our e-books. Our own printed books do not have these watermarks. TERMS & CONDITIONS This e-book may not be distributed. This e-book may not be modified in any way. This e-book may be printed for personal use only. No pages may be extracted or removed from this e-book. This e-book may not be included in any commercial package. This e-book may not be sold. Copyright © 2010 Forgotten Books AGorgotten Books FREE BOOKS www.forgottenbooks.org You can read literally thousands of books for freq at www.forgottenbooks.org (please support us by visiting our web site) © 2010 Forgotten Books www.forgottenbooks. orgForgotten Books takes the uppermost care to preserve the entire content of the original book. However, this book has been generated from a scan of the original, and as such we cannot guarantee that it is free from errors or contains the full content of the original. But we try our best! “Pow yay sc, het emt bs Resuty beng, fur nese ‘raed ect de Ca ths ure et hose opr Row shave decal Bieri preney. © 2010 Forgotten Books www.forgottenbooks. org© 2010 Forgotten Books www.forgottenbooks. org© 2010 Forgotten Books www.forgottenbooks. orgINTERNATIONAL CHEMICAL SHERI H. P. TALBOT, Pu. D., Consontine Eprror APPLIED COLLOID CHEMISTRY GENERAL THEORY © 2010 Forgotten Books www.forgottenbooks. orgMA My OM TTY um Me Graw Hill Book @.he PUBLISHERS OF BOOKS FORT CealAge vy Electric Railway Journal Electrical World v Engineering News-Record American Machinist v Ingenieria Internacional Engineering &|Mining Journal ¥ Power Chemical &| Metallurgical Engineering trical Merchandising © 2010 Forgotten Books www.forgottenbooks. orgAPPLIED COLLOID CHEMISTRY GENERAL THEORY BY WILDER D. BANCROFT PROFESSOR OF PHYSICAL CHEAUNTHY AT CORYELL UNIVERSITY First Epqrion McGRAW-HILL BOOK COMPANY, Inc. NEW YORK: 370 SEVENTH AVENUE LONDON: 6 & 8 BOUWERIE ST., E. C. 4 192 © 2010 Forgotten Books www.forgottenbooks. orgCopyricnr, 1921, ny THE McGraw-Hiit Booz Company, Inc. fo Marte PREAS YORE ra © 2010 Forgotten Books www.forgottenbooks. orgPREFACE The earlier books on colloid chemisiry presented the subject empinically because no other method was then possible. While we dq not now know much about gelatinous precipitates and jellies, the theory of the rest of the subject is in fairly good shape and cpnsequently T have written this book deductively. While any point of view differs considerably from Freundlich’s, it is a pleasure to acknowledge my debt to him for what he did in his adinivjable book. This volume on general theory should be followed by at least one volume on each of the following subjects: silicate industries; paints and varnishes; plastics; fibers and dycing; photochemistry and photography; petroleum industries; ore flotation and allied subjegts; foods and beverages; soils and crops; biology and medi- cine. | Allowing a minimum of three years to a volume, it scems very Improbable that I shall write all of these single-handed. With the general theory of the subject, once cleared up, there is no yeasom why the other volumes should not be written by people whosq knowledge of the special subjects is much greater than my own. I am indebted to Messrs. Bray, Briggs, Clowes, Holmes, Johnston and Lamb for reading the manuscript and for critical comnjents on it, Coxwent, UNtverstry, Nevember 1, 1920. © 2010 Forgotten Books www.forgottenbooks. org© 2010 Forgotten Books www.forgottenbooks. orgTABLE OF CONTEN’ Isrropuction . CHAPTER F Apsonpvion of Gas or Varor py Son... 2... Adsorption of Gas or Vapor by Solid... . The Adsorption Isothorm . 2. Chemical Reactions. ©. CHAPTER II ADSORPTION OF VAror bY Liguip, AND op Tiquip AND Sontp By Soup ANDIAQUID Adsorption of Vapor by Liquid... 2... Adsorption of Liquid by Solid... 0. 2... Adsozption of Solid by Solid. Adsorption of Liquid by Liquid Adsorption of Solid by Liquid . CHAPTER IIT ApsonPTION From Sontrion, . 2 2... Adsorption from Solution by Solid . The Adsorption Isotherm. . 2... 6. we Abnormal Adsorption . Le Negative Adsorption. 2... 0. ee Reversibility of Equilibriam , Spotificity of Adsorption . .. Adsorption of Several Solutes .. . Chemical Action. . . . Adsorption from Solution by Liquid CHAPTER IV Surnrace Tension—BrowN1aN MovEMENTS Adsorption and Surface Tension . Brownian Movements CHAPTER V COALRSCENCE 2 6 0 2... Se Coaleseonee of Liquids. se ee Coalescence of Solids . .- Types of Precipitates 2... oe Theory of Peptization . 0 0. 0 ek Bt Se 14 .. 14 » 14 ~ AGL . 166 © 2010 Forgotten Books www.forgottenbooks. orgCON ENTS CHAPTER VI PREPARATION OF CotLomaL Souuri Condensation Methods . Dispersion Methods CHAPTER VU Propermizs of Cornorpan SoLcrto} General Properties . . Viscosity . Color, : Electrical Properties |. Stability of Culloidal Solutions. CHAPTER VIL Jetuies anp Grvatixous Precieira Structure . sae Vapor Pressure Relations - Diffusion. . CHAPTER IX Enurstons axp Foams . . Ennulsiuns. .. Foams . CHAPTER X Non-aqueous CouLoipar Souution: CHAP! Foc axp SMOKE . . Fog Smoke . Precipitation of Solid ER XT CHAPTER XIL Gases ann Souivs In Sonins Gases in Solids. Solids in Solids CHAPT ‘THtokNyss or Surracy Finus Aurion INDEX. Svnseer Ixpex JER XII © 2010 Forgotten Books . 182 oe. 182 oes 190 . 196 206 . 212 OT . . 278 - . 286 » B00 » . 8OL . 304 305, sit B2b oe . 883 www. forgottenbooks. orgAPPLIED COLLOID INTRODUCTIO} In 1861 Graham! pointed out that s' hydroxide, potassium sulphate, magi and alcohol diffuse much more rapid. Lf. VHEMISTRY IN bstances like potasstuin esium sulphate, sugar, in water than hydrous silicie acid, hydrous alumina, starch, dextrin, (he gums, albumin, tannin, gelatine, ete. Since these latter] in a non-crystalline or even gelatinous calling them colloids from the Freneh we which diffused rapidly were to be called of them crystallized readily. Graham bel between a crystalloid and a colloid was to some molecular condition. Though begins with Grahain,? his distinction colloids has been dropped. A colloidal sarily amorphous, for colloidal gold is| times and possibly always. We now s| instead of a colloidal substance, and we when it is sufficiently finely divided or mitting ourselves definitely as to what necessary in any particular case. T often ealled the internal or dispersed p| phase the external phase or the dispe rain drops are the dispersed phase ay phase, while the solid particles are the i of smoke. When a milky liquid is ol barium sulphate in the cold, the barium ' Phil, Trans, 161, 183 (1861); Jour. Chem (1864). 2 Interesting work was done by Selmi in 184 effect on the development of scientific thought 3Cf. Wolfgang Ostwald: Grundriss der Koll 1 © 2010 Forgotten Books substances occur usually form, Graham suggested rdforglue. Substances rystalloids because many ieved that the distinction ndamental and was due modern colloid chemistry etween crystalloids and substance is not neces- certainly crystalline at cak of a colloidal state call any phase colloidal ldispersed,? without com- degree of subdivision is he subdivided phase is hase and the enveloping ing phase. In fog the d the air the dispersing ternal phase in the case tained by precipitating sulphate is the dispersed Boc., 15, 216 (1862); 17, 318 I; but it had no appreciable idchomic, T9 (199, www. forgottenbooks. org2 APPLIED COLLOID CHE phase and the solution the dispersing ph: in water, the oil is the internal phase b drops. When benzene is emulsified to amount of soup and water, we have a m phase in a viscous mass. Bread or Iv sidered as a system with air as internal external phase. In a porous plate or a fin are, op may be, continuous and it is th these as interlacing systems. True rub; as dispersed phase in glass as a nou-crys With salt colored by exposure to cathod sodium as internal phase in an extern sodium chloride. Adopting the very flexible definition t Joidal when it is sufficiently finely divid the chemistry of bubbles, drops, grain: because in each of these eases at least ons is very small. ‘This is not a truly seienti: a bubble has a film round it and a fil made up of coalescing drops or grains. fication, however for many purposcs. ESTRY se. In emulsions of oil ecause it is present in solid jelly in a small vile liquid as dispersed ry soap might be con hace, and a fairly solid fe sponge the two phases refore better to classify glass consists of gold alline dispersing phase. rays, we have metallic | phase of erystalline at 2, phase is called col- d, colloid chemistry is » filaments, and films, dimension of the phase fic classification because may be considered as It is a convenient classi- At first sight colloid chemistry may not seem to be an important branch of chemistry, either theoretically or technically; but thi we consider that a knowledge of colloid anybody who really wishes to understan: pottery, porcelain, glass, enamels; oils, glue, starch, and adhesives; paints, vari celluloid, and other plastics; Icather, p: easis, pencils, and crayons; inks; roa asphalt; graphites, patines; zinc, phosph num; contact sulphuric acid, hardened wine; cream, butter, cheese, and’ cas washing, dyeing, printing; ore flotation, is opinion changes when hemistry is essential to about: cement, bricks, greases, soaps, candles; ishes, lacquers; rubber, ‘per, textiles; filaments, ds, foundry cores, coke, rus, sodium, and alumi- ils, etc.; beer, ale, and ine products; cooking, water purification, sew- age disposal; smoke prevention; photography; wireless ielegraphy ; iluninants; comets; pharmacy; physiol colloid chemistry is the chemistry of ever © 2010 Forgotten Books logy. In other words, y-day life. www. forgottenbooks. orgci HAPTER I ADSORPTION OF GAS OR VAPOR BY SOLID ADSORPTION OF In an extremely subdivi relatively to the mass of thi to diseuss the propertics of of solids in contact with g adsorb, or condense upon thi which they are in contact. conditions of pressure and and physical state of the solf other words, the adsorptio! same solid and the same gag the higher the pressure of th| Hunter! showed that many} (tas on Varor py Soup led phase, the surface is very large phase and it is therefore advisable urfaces, beginning with the behavior lascs or vapors. All solids tend to cir surface, any gases or vapors with The amount of adsorption for given temperature varies with the nature id and with the nature of the gas; in is specific or selective. With the the amount of adsorption is greater gas and the lower the temperature. diflerent gases and vapors are ad- sorbed by charcoal to a matked extent. While his experiments are probably not very accurate, and are not made at strictly comparable temperatures and pressures, they cover more ground Some of his data are given in me data by Dewar? with cocoanut The volumes of gas adsorbed standard conditions; in other words sorbed gases would cecupy at 0° and —185° and 760 mm the actual vol- be only 88/273, or approximately nin Table IT. This correction was work. than those of anybody else. Table I. In Table II are charcoal at low temperatures. have been calculated back t to the volumes which the a 760 mm pressure. ‘Thus at! umes of gas adsorbed woul one-third, of the values givd not applied by Hunter in hi 1 Phil. Mag. (4) 25, 364 (186. 160, (1867); 21, 186 (1868); 23, 7 ® Proc. Ray. Soc., 74, 124 (190 ); Jour, Chem, Soe. 18, 285 (1865); 20, (1870); 24, 76 (1871); 25, 649 (1872). Bs. 3 © 2010 Forgotten Books www. forgottenbooks. org4 APPLIED COLLOID CHEMISTRY ‘Taube L—AbsonpTion or Gases anp Vapors sy Cocoanvr ( Volumes gas adsorbed per volume charcoal. ‘Temperature in Celsius degrees. Pressures in millimeters of mereury. HARCOAL Gas Yok. | Temp. re Gas Acetic acid. s3| 150 | 676 | Acetaldenyde j Water... at! 150 a4 | Acctaldehyde Water. aa) 128 | 624| Ammonia... Bongenw... so) 130 | 646] Ammonia....., Ethyl aleobol... si] 160 | 063 | Ammonia. Ethy! aleokol... ur] 127 { 644 | Ammonia... Ethyl aleoho! 1} 100 | 652] Ammonia Ethyl acetate. .. 72/154 | 659] Ammonia...., Carbon tetrachloride..| 4) 185 | 895 | Ammonia. Carbon tetrackloride,.) 8 | 100 | 626 ] Cyanogen. ‘Methyl aleokol 81] 150 | G84 | Cyanogen... Methyl aleokol. . 127 | 129 | 663 | Cyanogen. Methyl alcohol rot | 100 | 952 | Cyanogen. : Chloroform. 21 | 159 | 660 | Cyanogen Chloroform. 30} 100 | ast | Cyanogen Acetone... ax | ist | 67r | Hydrechloric acid Acetone ceeee-{ 105} 100 | 642] Nitrous oxide Carbon bisulphide 91) 158 | 639 | Carbon dioxide, Carbon bisu!phide ui7| 100 | 671 | Carbon dioxide. Bihyl ether... 64 | 180 | 688 | Nitrogen Ethyl ether..... 6g | 128 | 661 | Hydrogen Bithyl ether... s7! 00 | 64a ! Tarus IL—Ansorprion or Gases py Cocoanut Ciarq} Volumes gas adsorbed per volume charcoal. Pressures not given; volumes corrected to 0° and 760 mm. Temperature in Celsius degrees. aL. Gas Vol. I Temp. Gas _ a | Argon. | 32 | 6 | Nitrogen... Argon... 175 | —185 | Nitrogen. Oxygen... 18 Go | Hydrogen Oxygen... 230 | ~185 | Hydrogen.. Carbon monoxide a1 | 0. | Heliam...... Carbon monoxide... 100 | —185| Helium......... In Table IL] are given some more recent data by Hel Vaier,? who used a special animal charcoal, which they] 1 Zeit, Dlektrovbeoamie, 18, 724 (1912), pel and mixed to © 2010 Forgotten Books www. forgottenbooks. orgADSORPTION OF GAS a stiff paste with ox-blood dilut they then charred at 600°. ‘Paste IIL—Apsorrtion or G, Volumes gas adsorbed pez volume Volumes probably corrected to 0° OR VAPOR BY SOLID 5 ‘d tenfold with water and which ses ky Syxtueric Cuarcoan yynihetic 600° charcoal. nd 760 mm. —7R* | 183° i +20° 19.5 | 288.7 | es | 213.0 107.4 | 632.2 | Ch | 304.5 139.4 | 607.0 | NH: | 107.0 122-4 bese So, | 337.8 Ts? | +20° | Ne oa 92.6 | CH, | 41.7 | 174.3 NO. 103.6 | 231.8 | Gk. | 139.2 | 360.7 NO... | 109.4 | 830.1 | CoHs | 119.1 | 275.5 CO, s3.s | fos 4 | Gell, | 185.8 | 488.5 i Tasue IV.—Bouixe-voutrs or Various Lioiws Tiauid | BPs Liauid | BP. Liauid | B. Pt. Cae -s¢ | CH.CHO| +20.8 Hcl “82.9 | (CaHl}.0 | $34.8 CoH, —82.4: | CS, | 446.2 CO. -7 | Bra | $58.6 HS -60.2 1CHC | 461.2 Ch -33.7 | CHOW | 464.7 NH: -33.5 | COL 476.7 (CN), | -21. | C:H,OH | 478.4 Cai. . 801 =10. | OcHe +802 NiO. HO 100.0 For purposes of reference ther are given in Table 1V the boil- ing-poinis of some of the substances whose adgorption by carbon has been studied, Asa first app: @ gas or vapor is adsorbed mor point. Thus helium is taken up drogen, and hydrogen again is 1 Sublimation point: toximation it is often stated that readily the higher its boiling- by charcoal much less than hy- dsorbed to a much less extent © 2010 Forgotten Books www. forgottenbooks. org6 APPLIED COLLOID CHEMISTRY than nitrogen or oxygen. Carbon dioxide is adsorbed | less readily than ammonia, so that these substances follow the] em- pirical rule. Argon, however, is adsorbed less completely by chareoal than is nitrogen, while carbon monoxide is adsorbed to a greater extent at 0° than either argon or oxygen, though according to the rule this ought not to be so. Nitrous one is adsorbed less strongly than ethylene, and nitric oxide more strongly than methane, which is not according to the boiling- points. Ethane, ethylene, and acetylene are adsorbed more at +20° than is carbon dioxide, though the last is the most readily condensible gas of the four. ‘The difference between carbon di- oxide and hydrogen sulphide is in the right direetion; but seems out of all proportion to the difference im boiling-points. Hydrogen sulphide is adsorbed more than ammonia, which is wrong; and chlorine is adsorbed much more strongly than ammonia, although the two boiling-points are practically identical. Cyanogen is ad- sorbed more than ammonia at 70° and less at 0°. In the case of vapors there is no relation between boiling-point and adsorption. Going from higher to lower boiling-points, we have the order: water, benzene, ethyl alcohol, carbon tetrachloride, methyl 2cohol, chloroform, ether, and aldehyde. The order from greater to lesscr adsorption is methyl alcohol, ethyl alcohol, aldehyde, cther, benzene, water, chloroform, and carbon tetrachloride. |The truth of the matter is that adsorption is specific and varies with the nature of the gas and of the adsorbing solid. One charcoal is not like another. In Table V are Hunter’s results on charcoal ‘Tarte V.—Apsorption or Gases By CuancoaL yrom DirFERENT Woops Volumes gas adsorbed por volume charcoal. Temperature = 0°C; pressure = 760 mm. Wood Nib | C2 | Gch. Wood ik] 08: | (GR, — i Logwood.........] 111] 65 | 87 | Jamaiea logwood....| 69] 38 Iubony..... -| 107147 | 90 | Sapan wood. . 70} 32 Camwood. +f OL) 45 Beech. . 53) Green ebony,....| 90] 41 Rosewoo .| 51 Fustio (Cuba). ...) 90] 58 Wistaria sinensis 44 Tignum vite...) 89] 47 Vegetable ivory... ..| . - | 60 87 Boxwood... +. 86] 31 29° | Cocoanut shell...... 176! 71 414 i ee © 2010 Forgotten Books www.forgottenbooks. org,ADSORPTION OF GAS OR VAPOR BY SOLID 7 made from different woods. The cocoanut charcoal has the greatest adsorbing power of all and, of the others, logwood char- coal has the greatest adsorbing action on ammonia, fustic charcoal on earbon dioxide, and ebony chareoal on eyanogen. 1 is not the most porous chareoal in the ordinary sense which adsorbs the most gas, because Hunter says that the charcoal made from the shell of the cocoanut is very dense and brittle. The pores are quite invisible and, when the charcoal is broken, the fracture presents a semi-tnetallic lustre. It has been suggested by De Saussure! that charcoals with very many pores of very small diameter are the |best adsorbers because they present the larg- est. surfaces for condensation. This is not quite right because there are other factors besides the extent of surface, among them the arrangement of the surfaces. A plane surface will adsorb a given amount of a gas under standard conditions, but two plane surfaces placed elose to each other will apparently adsorb a good deal more gas than the same surfaces would if each did not, re-enforce the other and inodify the concentration gradient. The adsorption depends not only on the surface but on the structure of the the adsorhing material. Narrow pores, down to a cer- tain limit, should| adsorb more than spherical pores of large dia- meter and this actually happens. Table VI shows the change in the adsorption of air? when different charcoals are heated from -100° to +500°. | In a number of cases the parallelism between density and adsorption holds but by no means in all cases. While there may} be an actual difference in the amount of sur- face, we are uncoubtedly dealing with another factor, the pres- ence in the charcoal of substances which affeet the adsorption. Charcoal is far fiom being pure carbon and the great improve- ments in chareoal as used in warfare have been along the linc of cleaning the charcoal very thoroughly in addition to increasing the surface. While cocoanut charcoal is usually considered the best, the sour cherry charcoal in Table VI does better; and the synthetic charcoal of Hempel and Vater* was better than the best. cocoanut charcoal which could then be obtained, though far inferior to the best cocoanut charcoal of today. The varying 1 Cf, Dewar: Pree. Roy: Inst., 18, 180 (1905), * Prurri and Maqdiia: Gazz. ehim. ital., 40 I, 569 (1910). 3 Zeit. Elektrochemie, 18, 724 (1912). © 2010 Forgotten Books www.forgottenbooks. org8 APPLIED COLLOID CHEMISTRY behavior of charcoal from cocoanut shell, logwood, fustic, and ebony is probably due to the presence of different impurities which affet different gases in different ways. Paste VL—Benaviorn or DirreruNT CHancoaLs ne RAS per or charcoal — 100° Ceratonia siliqua Prunus armbniace. . Juglans regia. Pinus rigida..........| Piteh-pine : Bit4 Robinia pseudo-acacia.’ Common locust... 1.2218 .| Apricott....... English walnut 3004 3132 Apparent to +550" nay ! | Air | Ch i | Prunus cerasus ...... | Sour cherry?.. 1. 290.1 | 312.7 Cveus nucifera........| Cocoanut? .. 1. 251,38 | 3342 Phillyrea media. ...../ Jasmine box 1. 222.4 | 260.0 Grevillea robusta. Silk oak...... 1. 212.7 Abies alba .| White spruce 1. 199.5 Castanea vesea.......) Enropean chestnut ..| 1.3 186.3 Buxus sempervirens. ..| Common box.......| 1. 138.5 Liospunos kaki........| Chinese persimmon .| 1. 134.5 Populus nigha. . | Black poplar. 1.2802 | 134.1 Prunus virginians 1. 133.0 1 3 1 5 1. 6 1 1 0 Charegal is used in most gas masks, beeause it is the best all- round adgorbent for toxic gases.2. The removal of the toxic inaterials must be surprisingly complete. The adsorbent must be capable of reducing the coneentration of the toxic gas from, say 1000 p.p.m.? to L p.p.m. or less within the 0.1 second that the air takes in passing (hrough the canister. This is accomplished with a safe margin by the present gas mask matetials. In fact it has bean shown that charcoal will reduce a concentration of 7000 p.p.m. of chloropierin, CClzNOs, in a rapidly moving eur- rent of aim to less than 0.5 p.p.m. in something under 0.8 seconds. Some use has been made in peace times of the fact that properly 1 Shells and kernels, 2 Lamp, Wirson aud Crave y: Jour, Ind. Eng. Chem, 41, 420 (19)9). * Parts por million by \olime © 2010 Forgotten Books www.forgottenbooks. orgLION OF GAS OR VAPOR BY SOLID 9 prepared eharepal will adsorb gases to a eonsiderable extent. Melscus' placed wood charcoal, saturated with dry chlorine, in the longer braneh of a bent scaled tube and dipped that end of the tube into boiling wator, while the shorter branch was placed in a freezing mixture. A portion of the gas was volatilized and the presstre thus developed eaused liquefied chlorine to appear in the cold portion of the tube, Sulphur dioxide, hydrogen sulphide, hydrobremie acid, and cyanogen can be liquefied in the same way;|but not bromine, hydrochloric acid, carbon bi- sulphide, ether, |or alcohol. In 1874 ‘Laip and Dewar* described the use of charcoal as a means of getting a high vacuum. They placed a piece of char- coal in a tube having platinum electrodes, heated the tube to a red heat, exhausted it with a Sprengel pump and sealed it. If the tube was eopl, no spark would pass when using an induction coil capable of giving a quaricr of an inch spark. On heating the tube slightly some gas was given off fron the charcoal and the spark passed, By making use of the increased adsorption at low temperatures qhite surprising results were obtuined.? A bulb of 300 ce eapaqity, containing air at 15° and an initial pressure of 1.7 mm, was|eonnected with another bulb holding five grams of chareoal. When the charcoal was cooled in liquid air, the pressure dropped to 0.00005 mm. A Crookes radiometer tuhe, filled with hydfogen st atmospheric pressure, had a charcoal bulb attached. | On dipping the charcoal bulb into Liquid sir, no rotation took place even when the beam from an electric are was focussed op the vanes. The motion became quite rapid however when the charcoal bulb was placed in liquid hydrogen because the adsorption of hydrogen by charcoal is sufficient at these very low bempcratures, though not at the temperature of liquid air. The adsorption of helium by charcoal at -252° is not enough to make this experiment suceessful when the radio- meter tube is filled with helimn. Sinee different gases are adsorbed in different amounts, the ratio of two gases in the charcoal will differ from the ratio in the gas phase and| a separation will be possible to some extent. + Comptes rendifs, 77, 781 (1873); Jour. Chem, Soc., 27, 120 (1874), * Proc, Roy. Nod. Kdin,, 8, 848, 628 (1874). 2 Dewan: Proe| Roy. Inst., 18, 437, 756.(1908). © 2010 Forgotten Books www.forgottenbooks. org10 APPLIED COLLOID C. Dewar! heated about 50 grams of lj it nf -185° in a current of pure dry a The vessel contaming the charcoal was taken out of the liquid air and ‘The volumes of gas givel liters respectively and the oxygen eq Tl at 76 mm, and at 5 mm, rise to 15°. larly between 56 and 58 percent. practical constancy of the mcan coi EMISPRY arcoal and then saturated ir at atmospherie pressure, lhe temperature allowed io » off were 5.7, 4.8, and 4.5 centration varied irregu- hese experiments show the position of the gases ad- sorbed by the charcoal under the conditions of these experiments and they therefore show that wide ch: air current have but slight effect in al tions of the adsorbed gases. In ano containing the saturated charcoal wag containing a little liquid air so that slowly. Table VII. The mean composition Tasun VIL—Distinnation oF Am This made it possible to coll the successive lilers of gas as evolve] inges in the pressure of the tering the relative propor- her experiment the vessel placed in a vacuum vessel Ihe temperature might rise ject and analyze separately dl. The data are given in f the six liters was 56 per- ADSORBED BY CiancoaL First liter... ... | 18.5 percent O+ |Fourph liter......; 72.0 percent Or Sceond liter.......| 20.6 poreent O+ | Fifth] liter... 79.0 percent O» ‘Third liter .| 83-0 percent O, |SixtHliter.......] 84.0 percent 02 eent oxygen. mixtures of nitrogen and oxygen. A few experiments wi Wi ing 6.5 pereent oxygen was used ani rapidly to 15°, five liters of gas were cent oxygen. At higher temperatures the results though this may be due to the remov. Skey? found that red-hot chareoal nitrogen which is given off when the ¢ in water. Storey and Lewis? state { adsorbed nitrogen and carbon dioxid 1 Proc. Roy, Soe., 74, 126 (1904); Proc. B * Chem. News, 15, 15, 27 (1867). * Am, Chem, Jouz., 4, 409 (1883). © 2010 Forgotten Books of re also made with special en a gas inixture contain- the charcoal was heated tained, containing 28 per- em to be quite different, 1 of oxygen by combustion. jains over three volumes of oled charcoal is immersed hat it is difficult to remove from coke even by heating ‘oy. Inst., 18, 184 (1905). www. forgottenbooks. orgADSORPTION OF GAS OR VAPOR BY SOLID 11 the containing fla: k to 200° and exhausting with a Sprengel pump. In these two cases the oxygen was probably burned com- pletely. It is not results. He heat} to 140° in @ para: given off. With trogen. After the the evolved gas 9.2 percent CO2, charcoal consisted that from crushe percent Nz and 2) ash yielded a gas ¢ so easy, however, to account for Blumtritt’s pd various forms of charcoal under mercury fin bath and analyzed the gases which were ommon wood-charcoal the gas was pure ni- same charcoal had been moistened and dried, tontained 85.6 percent Na, 2.1 percent Os, hnd 3.1 percent CO. The gas from poplar of 83.5 percent N», and 16.5 pereent COs, d alder charcoal had the composition 78.9 +1 percent CO2, while charcoal made from nsisting of 76.0 percent Ne, 9.1 percent COs, and 14.9 percent Og. These variations, if real, probably depend on the nature and coal; but the expe: Jena flask filled wii analyzed the cont nitrogen and so W oxygen had oxidi: burning it to CO o In Dewar’s expel apparently given ot tion with CO or C temperatures, whe! coal were heated % duced into a cylin} measured volume undoubtedly coole contact with the 9} ficd himself that n| in the cube of chi mount of the hydrocarbons left in exch char- iments should be repeated. Craig? heated a rh lignite coke to redness, closed the flask and nts, The unadsorbed gas was nearly pure las the adsorbed gas, which meant that the ed some unspecified hydrocarbon without COs, ‘iments the oxygen adsorbed at —185° was at —15° without any appreciable contamina- 2. Calvert’ observed no reaction at ordinary carefully purified pieces of boxwood ehar- redness and, while still red-hot, were intro- ler standing over mercury and containing a of oxygen. Passing through the mereury the charcoal a great deal before it came in ygen. By special experiments Calvert satis- carbonie acid had been formed, or existed, coal. Since the adsorbed oxygen oxidized ethyl aleohol to acetic acid, and ethylene to carbon dioxide and water, It is certain) in analysis, becans mouoxide or carbo: 1 Jour, prakt. Chem| 2 Chem. News, 90, 3 Jour, Chem. Soe., that there cannot have been a serious errer such oxidations could not be caused by carbon h dioxide. |, 98, 418 (1886), og (1904), 120, 203 (1867). © 2010 Forgotten Books www.forgottenbooks. org12 APPLIED COLLOID CHEMISTRY Quite different results were obtained by C. J. Baker’ working with purified blood charcoal which was allowed to adsorb oxy- gen at —15° and was then pumped out. On heating the tube to 100° seven volumes of CO, were obtained when oist Oxygen was used, while no gas was given off when dry oxygen was used. In a check experiment it was shown tbat no carbon dioxide was formed when water vapor and earbou were heated to 100° in a sealed tubs for a week. The question arose whether dry oxygen was adsorbed or whether it was held more firmly than moist oxygen. Practically no gas was given off up to 350] regular stream of gas was given off which consisted » Ab450° a f 99 pereent CO and 1 percent CO, in those cases where the drying had not been done so carcfully. Intermediate values wel re found for intermediate degrees of drying. WRhead and Wheeler? do not confirm Baker’s results though this may be beca their experiments differently. Rhead and Wh: nse they did eler treated purified carbon at some definite teinperature, 200P, 300°, ete., with air, pumped out the air, and then heated the charcoal more or less rapidly to 2100° and analyzed the gas. With an initial temperature of 300° and rapid heating to 1100° the composition of the evolved gas was 11.3 percent CO, and 88.4 pereent CO when dried air was used, and 15.4 percent CO plus 84.4 pereent CO when moist gas was uscd. When the initial was 300°, the gas coming off between 300° and 400° ¥ temperature as composed of 57.0 percent COs and 42.4 percent CO; between 400° and 500° the composition was 41.6 percent CO: and 58.0 dropping to 0.8 percent COz and 98.7 percent Ci drawn off between 800° and 1100°. Baker found J and 99.0 percent CO at 450°; but his initial tem. — 12°. The tivo sets of experiments should be rep we tight know whether they are or are not ¢| Neither Rhead and Wheeler nor Baker found any gas given off above 200°. By determining the oxi at different temperatures of charcoal containing a} gen, it should be possible to determine approxim: . temperature all the oxygen was converted into In spite of all the exevlient work that has been don ‘Jour, Chere me BA, 249 (1887), (hid., 103, "wl. Wid) (Lutsty © 2010 Forgotten Books percent CO, for the gas percent COs perature was ated so that ntradietory. xygen in the izing action dsorbed oxy- jtcly at what 10 and CO.. on the con www. forgottenbooks. orgADSORPTION OF GAS OR VAPOR BY SOLID 13. bustion of carbon, there is still a great deal that we do not|/know. ilulett has found that there is a slow reaetion between oxygen and charcoal at ordinary temperatures, apparently the formation of 2 non-volatile oxide. When one blows a slowly dying wood fire with the bellows, (he fire will often start burning briskly again, in spite of the fapt that the large influx of cooler air must tend to chill the embers and thus to put the fire out. Bacon! suggests that the dying embers are covered with an adsorbed film of carbon dioxide which ig swept sway to some extent by the draught from the bellows. | When the fire is burning briskly, there is less carbon dioxide adsorbed at the higher temperature and the natural draught is suffieicnt to bring oxygen to the burning wood. Though this hyppthesis has not been proved, it is rendered more probable by the experi- iments of Arndt and Sehraube,? who found that even af a red heat carbon dioxide is adsorbed more strongly than carbon mon- oxide or nitrogen. Manville’s fluctuations of ihe ignition) point of charcoal* are probably duc to hydrocarbons which hhd not been removed. Ramsay* has availed himsclf of Dewar’s method of using cooled cocoannt charcoal as an adsorbent for gases to detbrmine the amounts of neon and helium in the air. At 100° the axygen, argon, and nitrogen are taken out practically quantitatively while the adsorption of neon and helium is negligible. At/—185° practically all of the neon is adsorbed and none of the helium. From his observations, Ramsay concludes that the contentra- tion of neon in the air is about 0.00123 volume perecnt and)that of helium about 0.00044 volume percent, while the amount of free hydrogen cannot be greater than one five-hundredihl of the combined volumes of the neon and helium. At great cleyations this changes completely, the gas with the lowest mdlecular weight concentrating in the higher regions. Alleman] gives some data for the estimated concentrations of hydrogen at different heights above sca-level, Table VIII. 1 Jour. Phys. Chem., 17, 768 (1913). 2 Nernst Festschrift, 46 (1912). 3 Jour. Chim. phys., 6, 297 (1907). 4 Proc. Roy. Soe, 76A, 111 (1905); BOA, 599 (1908). ® Jour. Franklin Inst., 185, 161 (1918). © 2010 Forgotten Books ‘www.forgottenbooks. org14 APPLIED COLLOID CHEMISTRY Tasre VIL.—Esrinarep Distriauvion oF HYDROGEN IN THE ATMOSPHERE oe a oe a 140 99.2 0) O47 20 0.04 130 99.0 70 32.6. 1b 0.02 120 98.7 60 10.7 ll 0.01 110 98.1 50) 2.80. 5 0.01 100 95.6 40 0.67 96 883.3 | 30 0.16 Dewar! has worked out a very effective lecture experiment, based on the selective adsorption by charcoal, A number of Spectroscopic tubes, connected in series with a large U-tube con- taining charcoal are exhausted by cooling the charcoal until the electric discharge will barely pass. The chareoal tube is now laced in liquid air and a current of air is allowed to enter the ystem slowly, passing first through the charcoal tube which fk out the rendity adsorbed gases such as oxygen, nitrogen, md argon, while helium, neon and hydrogen pass through. When the pressure in the first (ube has risen sufficiently it begins 0 glow with the well-known rich orange hue of neon. In time he characteristic discharge of neon and helium appears in the ther tubes. The sensitivencss of the neon tubes to induced electric oscillations from a coil of wire placed at right angles to fhe tube may be shown. Claude? points out that the remarkable luminosity of neon can be utilized for lighting purposes. One of the difficulties of the problem is the ease with which neon is masked by small quantities of certain other gases. It is not enough to introduce very pure neon into a tubo with electrodes inder suitable pressure in order to obtain an effectively luminous ube. This can be overcome by removing these other gases with cooled charcoal, when the beautiful orange luminescence of eon appears, and retains its brightness. The light is very rich ur red rays and Claude considers it just the corrective required or the light of mereury vapor tubes. 1 Proc, Roy. Inst., 18, 444 (1906). * Mon, Sei., 74, 135; Jour. Franiclin Inst...171..024.(1911). © 2010 Forgotten Books www.forgottenbooks. orgADSORPTION OF GAS OR VAPOR BY SOLID 15 Krypton and xenon may be obtained from the air by means of cooled chareoal.t A current of air passes through a series of tubes immersed in liquid air for the purposes of purification, the last tube containing cotton wool in order to retain any dust of the solid, condensed impurities. This pure air is passed through a tube containing about 100 grams of charcoal for at least 24 howrs. The charcoal tube is then removed and placed in solid carbonic acid, and the gas which is evolved is allowed to escape. he Bs remaining in the charcoal at — 78° is driven off by heat- ing and exhaustion, and all the carbon compounds and oxygea remaved from it. The remaining gas, consisting of nitrogen, krypton, and xenon, is separated into its constituents by conden- sation and fractionation. Instead of passing a current of air over|charcoal at. — 183°, a few hundred grams of charcoal may be covered with liquid air and the latter may be allowed to evaporate in a silvered vacuum vessel. The gases remaining in the charcoal can then be separated as before. In this way spec- trum tubes of krypton and xenon may be readily prepared. Ruthorford? found that cocoanut charcoal adsorbs radio-active emanations. A slow current of air charged with the emanations of radiurn, thorium, or actiniumis deprived of some or all of its emanation in the passage through a tube filled with cocoanut charcoal, and for this purpose the charcoal need only be at ordimary temperature, The complete withdrawal of the eman- ation only takes place when the air is passed very slowly through the charcoal; if the speed is increased, the amount of unadsorbed emanation increases also. In another experiment Rutherford found that if'a tube containing less than a gram of charpoal is connected to a vessel containing thcemanation from several milligrams of radium bromide, the charcoal will adsorb the emanation in time. If some powdered willemite be mixed with! the charcoal, the gradual adsorption is shown by the inercas- ing |brilliancy of phosphoresecnce of the willemite, Tt is not nevessary to heat or exhaust the charcoal previously; but if this is done the emanation is adsorbed more rapidly. ‘The charcoal retains the emanation at ordinary temperature but the greater I Vacentwwen and Scrmtpr: Sitzungsber. Akad. Wiss. Berlin, 1905, 816; Dewan: Proc. Roy. Inst., 18, 443 (1906). 2 Nature, 74, 634 (1906) © 2010 Forgotten Books www.forgottenbooks. org16 APPLIED COLE part of it is expelled by heating FD CUBMISTRY joalowredheat. Boyle 'showed that cocoanut charcoal adsorbed thorium emanation the most and ordinary charcoal the least between the other two. The much when cocoanut charcoal slightly in the case of wood chi coal begins to give off carbon dio} adsorbing thorium emanation up| for the charcoal to become sati as may happen with other gase: adsorbed by the chareoal is de in 54 seconds. The general rule for mixture , while animal charcoal caine in ate of adsorption increased very was used at —75.5° and only reoal, At 211° cocoanut char- ide; but it shows some power of lalmost{0300°. Itis not possible rated with thorium cmanation , because the thorium emanation aying at the rate of half-value is of gases seems to be? that the more readily adsorbed gas displaces the other to some extent and is adsorbed to a greater relati predicted from experiments on universally truce. Bergtcr? fou Inm oxygen is adsorbed 30 to 4| and that at these pressures the amount of nitrogen adsorbed. ane may have ane of the vapors| Cases of this sort have been st ing instance being water and a: the adsorbed water dissolves or ing the amount of ammonia, a) It has beon shown by E. E. Rei benzene or cther in charcoal will chloropicrin, The data in Table TX are no} have them; but they do indica gas will cut down the adsorptio. parisons should be made at equal gas over charcoal which has a 1 Jour. Phys, Chem. 12, 264 (1903) also Narrenux: Phil, Mag. (8) 16, 5S Monst: Atti Acad. Lincei, 20 I, 932 2 Pesunpuicu: Kapillarchemie, 99] # Drude’s Ann. 37, 480 (1912). 4 Jour. Chiu, Sov, 23, 73 (L870). § Ibearne and Varn: Zoit, Wekt fe amount than one would have he single gases. This cannot be id that at pressures of 0.5 to 10 times as strongly as nitrogen, presence of oxygen increases the With readily condensible gases, helping to carry dawn the other. died by Hunter,* the most strik- imonia. It seems probable that ladsorbs ammonia thus increas parently held by the charcoal. id that the presence of traces of increase the service time against tabulated as one would like to ic that the presence of a second of the first,® though such com- partial pressures. Passing one sorbed another gas should theo- ; Phil. Mag. (6) 17, 874 (1909). Sce (1908); 20, 778 (1910); Poxsueza and asta). (1909). chemie, 18,724 (1912). |@ 2010 Forgotten Books www. forgottenbooks. orgADSORPTION OF GAS OR VAPOR BY SOLID 17 retically| cause complete displacement of the adsorbed gas; but it is evident that the effectiveness will be much greater if one dis- places the slightly adsorbed gas by the readily adsorbed one rather than the other way round. It would be very interesting to determine an isotherm showing the relative amounts of two gases in|the vapor phase and the charcoal phase when in equi- librium At constant pressure. ‘Taste IK.-~Apsorprion or Mixep Gases sy SyxvHeric Caancoan Mixed pases with 0.4 g synthetic 600° charcoal. Could ddsorb about 30 ce ethane, Hy: i Calls C:He adaorbed adsorbed ungdsorbed 95.0 6.0 5 37 3.7 15 45.0 5.0 10 i 3.8 7.6 2.5 20.0 5.0 20 3.8 15.2 5.0 Wa 5.0 30 44 26.4 TA 6.1 5.0 45 4.6 41.4 9.5 a | oy | tet om | ke | alten 95 0 5.0 | 1.3 95.0 6.0 3.6 15.0 5.0 2.7 15,0 5,0 4A 6.1 5.0 3.3 6.1 5.0 5.1 2.7 6.0 3.9 2.7 5.0 5.5 He | C2He i adsorbed Ne I CoHa adsorbed 95.0 5D 3.6 95.0 5.0 6.2 15.0 5.0 4.7 30.0 5.0 90.6 6.1 5.0 5.2 12.2 5.0 10.7 2.7 5.0 | 5.7 B.A 5.0 11.6 A curjous cage has been cited by Matwin.! Charcoal will take carbon bisulphide and carbony! sulphide out of illuminating gas, one kilopram of charcoal cutting the sulphur content of ten cubic meters pf gas to 2.92 grams. Porous charcoals are the best, 2 Jour, |Gasbcleuchtung, 62, 602 (1009). © 2010 Forgotten Books www.forgottenbooks. org18 APPLIED COLLOID CHEMISTRY such as pine and linden. Bone-black takes up almost no carbon bisulphide, and cocoanut charcoal is said to be even less effective. This is very remarkable, because cocoanut | charcoal adsorbs carbon bisulphide strongly. We must either assume that the illuminating gas cuts down the adsorption of |carbon bisulphide very much or that there is an error in the statement. If carbon bisulphide and illuminating gas were adsorbed] in the same ratio in which they oceur in the mixture, there would be no apparent purification even though the actual adsorption were very large.? This point ealls for more study. The adsorption of gases by charcoal has been studicd exten- sively, because charcoal adsorbs so many gases|and adsorhs them so strongly. Experiments have also been made with many other solids—silica, alumina, glass, wool, rubber, celluloid, meerschaum, metals, soils, ete. The behavior of glass is impor- tant because of its use in the laboratory, Mulfarth? states that the adsorption decreases in the order: NHs, SO2,NLO,C2H2. Kundt and Warburg’ found that a small amount of water is retained obstinately by glass even when the pressure is reduced practically to zero. In order to remove this water the glass must be heated, in which case one is likely to cause changes in the glass, setting free water vapor and gases that were not ad- sorbed in any proper sense of the term.4 On the other hand, -the film of water which usually covers glass surfaces is due chiefly to alkali dissolved from the glass.6 It is hard to tell whether the change in the vacuum of a Crookes’ tube is due to adsorption of the gas by the glass or not. Swinton® found that the inner surfaces of these tubes are roughened perceptibly after being subjected to cathode ray bombardment. When these portions of the tube arc heated strongly in a blow-pipe,| they immediately beeome clouded, owing to the formation of/ minute spherical bubbles which average about 0.01 mm in diameter. The centers 1Cf. Le:curon: Jour. Phys. Chem., 20, 32 (1916). 2 Deude’s Ann., 3, 328 (1900), * Wied. Ann., 24, 327 (1984); ef, Bunsen: Pogg, Ann, 156, 201 (1875). aeuenvore: Jour. Am, Chom. Sce., 40, 1645; Phys, Rev, (2) 22, 448 ® Warburg and Insxort: Wied. Ann. 27, 481 (1886); Inseorr: Tbid., 31, 1006 (1887). *Proe. Roy, Soc. T9A, 134 (107). © 2010 Forgotten Books www.forgottenbooks. orgADSORPTION Of GAS OR VAPOR BY SOLID 19 of th¢ bubbles are about 0.12 mm from the inner surface of the glass| The number of bubbles per square centimncter of glass was fbund to be about 625,000, or about 0.000133 ce of gas per square centimeter. The gas is mostly hydrogen and is given off when|the glass is powdered, It is not known whether the bubbles are connected with the inner part of the tube by minute channels or not. If they are, this isa case of adsorption. If the bubbles are a¢tually buried in the glass owing io the latter flowing round them] that is not adsorption. L. J. Briggs' showed that fincly divided quartz adsorbs water vapot, though not to the same extent as amorphous silica. Aboub 9 mg water was adsorbed at 30° by 50 ¢ quartz having an estimated surface of 20,000 cm? when the vapor pressure was 26.1 inm, about 4.5 mg when the vapor pressure was 19.6 mm, and about 0.5 mg when the vapor pressure was 0.2mm. Cohn- staedt? states that the gas given off by aluminum electrodes in a Crookes’ tube is water vapor and not hydrogen, as usually be- lieved. He elaims to prove that glass and aluminum gurfaces will retain water even when heated to 500° or when dried over phosyhorts pentoxide. It is the presence of a water film of varyibg thickness on a glass or other vessel which makes it necessary to keep the moisture constant if accurate weighings are to be|madc. Professor Morley once said that it was a mistake to believe that it is a difficult matter to dry a gas. That is a very simple thing to do; but the difficulty is to dry the vessel which holds|the gas. Drpeker and Ullmann? showed that the adsorption of a vapor by tHe glass containing vessel causes only a negligible error in vapordensity determinations with ether, aleohol, benzene, and chloroform; but the errer may amount to 2 percent with accti¢ acid at 80°. At higher temperatures the adsorption decrepses and the error is considcrably less. Thc adsorption of ammonia by solid ammonium hydrosulphide introduces a serious error|in the equilibrium relations for ammonia and hydrogen sulphlide.* } Jone. Phys. Chem., 9, 617 (1905). 2 Diude's Ann., 38, 223 (1912). 2 Zeft, phys, Chem., 74, 507.(1910). *Mhovussow: Jour. Phys, Chem., 11, 21 (1907). © 2010 Forgotten Books www.forgottenbooks. org20 APPLIED COLLOID CHH MESTRY While most solids, even though porous, do not adsorb gases as much as charcoal, yet Dewar! reports shows 2 remarkable power of acisorbing one gram condensing some 70 ce at atu adsorption by alumina decreases very pressure, and consequently alumina. ca: of obtaining high vacua. Meerschaum| what likealumins. On theothcr hand, bi by means of eopper powder.?- Carbon di are both adsorbed strongly by aluming. take up 100 volumes of hydrogen and 3000 volumes of hydrogen,’ but it is hydrogen is all adsorbed or is partly dij palladium, heated to 100°, is used to is purely a question of rate because eq rapidly at the highcr temperatures. report on the adsorption of acetylene black will take up more than 800 volum certain that some of the platinum has be adsorbs carbon dioxide® and rubber ap also other gases, though it is possible 4hj in the case of rubber. Wool'? adsorb: andamimonia gas. Robland'= reports pounds are adsorbed by clay and oxygel oxides of silizon, aluminum, iron and tit} If the film of condensed air on a sma. sac thickness irrespective of the diam| it does not decrease too rapidly with ratio of air film to mass of particle w: ‘Proc. Roy, lust., 18, 435 (1906), * Mincrow: Jour, Chem, See., 108, 645 (100) 4 SenuERMBssER: Centralblatt (3) 2, 165 (1 $Jouvson: Jour. Am. Chem. Sve., 34, 911 * Paap and Gerum: Ber. deutsch. ehein. G * ber. dentsch. chem, Ges., 43, 2684, 2602 ( ‘Eveunn and Wéntsr: Zeit. anorg, Chom *Lerenurs: Jour. Chem, Soe, 105, 328 (19. 2 Reverie: Van Beumelen Gedenkboek, “Feet spe: Iupillarcherie, 108, (1909) 4 Zeit. anurg. Chen, 68, 108 (L905). © 2010 Fo i Ihat dry aluminum oxide air at low temperatures, ospheric pressure. The rapidly with doereasing not be usec as a means and silica behave some- gh vacua cao be obiained loxide’ and water vapor? Platinum black may palladium nearly up to ot certain whether this solved. Tn gas analysis emove hydrogen. This librium is reached more Paal and Hohenegger® y palladium. Platinum 8 of oxygen; but it seems on oxidized.” Celluloid parcntly adsorbs® it and nt we have true solution both hydrochloric acid that unsaturated com- uated compounds by the nium, 1 particle remains of the rter of the particle or if eereasing diameter, the inercase as the particle 5). B70). 1912), ., 41, S05 (1908). 1910). |, 29 (1909). 4). [55 (1910), gotten Books www. forgottenbooks. orgADSORPTION OF GAS OR VAPOR BY grows sinaller. Cushman and Coggeshall! fou oowder whieh would pass through a 200 inesh Lliquid. When poured into a vessel, it only af the space, while a coarser powder filled more ising that the ab-eushion around each pai grains move one over another like a liquid. As ion has been observed with ground phosphate «tbstance like carbon black, which adsorbs gase: ws little as 5 percent of the apparent volume mal sarbon black? and a liter of carbon black may ¢: of air. When indigo is reduced to a very fine pe ou disintegrator’ the single particles appear SOLID 21 md that a rock ieve surged like led 46 percent Tt is not sur- iele makes the imilar phenome- rock, With a very markedly, be due to the niain 2.5 liters wer by means jo be separated me from another by an envelope of air, so that the dry, solid sowder occupies @ space equal to that of a 20 ndigo, containing the same amount of indigo. out that the freedom of motion of finely divide secomes more marked when there is a femperatu: sites the mobility impartcd to very fine powders} sium carbonate or precipitated silica by heating lish. When the dish is disturbed the powder g] joating whenever the powder is able by radiati ower temperature than the dish. Ives, Kingsbury and Karrer® siute that the ¢ shermocouples of varying diametcr ean be acco satisfactorily if it is assumed that they may 2ylindrical wires to which heat is conveyed the of hot gas, of thickness independent of the tem; of the wire. ercent paste of Stoney® points solid particles ic gradient. He such as magne- them in a metal ides about as if in to maintain a aracteristics of inted for rather ¢ considered as ough thiu films erature and size The presence of a film of air or vapor round a solid particle s shown in a striking way by the fact that it i natter? to pass suspended phosphorus pentoxide wash-bottles in spite of its tremendously hyg) Jour. Franklin Inst., 174, 672 (1912). 2 Canor: Eighth Int, Congress Applied Chem. 12, 18 3 Sauin: Technology of Paint and Varnish, 201 (1917). * Jour. Sov. Dyers and Colourists, 17, 294 (1901). + Phil. Mag, (5) 4, 443 (1877). 8 Jour. Franklin Inst., 186, 421 (1918). quite a simple through several poscopic nature. 1912). TEnouen and Winp: Ber: deitech, cher. Ges. 28. 1929 (1896). © 2010 Forgotten Books www. forgottenbooks. org22 APPLIED COLLOID CHEMISTRY ‘Tyndall! found it very difficult to get experimental tubes which were absolutely clean on the surface and which contained no suspended |particles. Dust-motes from the external air passed through Ultubes containing potash and sulphuric acid and through flasks containing ethers or aleohols. He states that it requires Iong-continued action on the part of an acid, first to wet the motes and then to destroy them.? The difficulty in stopping smokes in gas warfare is that the particles do not come in contact with the materials in the mask. Schlocsing’ has put the thing generally by saying that it is much easiet to take gas out of a gaseous mixture than to remove suspended liquid or solid particles. If the sheath of adsorbed air or gas is ramoved, wetting may take place. Since the sulphur trioxide from the contact process can be caught in concentrated acid and ndt satisfactorily in water, the concentrated acid must displace inp gas film rapidly and fairly completely, while water does not; but we do not yet know the reason for this. One can- pot agree with Knictsch* however when he says that it is a very remarkableljand not satisfactorily explained fact that the sulphutie acid fog from the burner gases is more difficult to precipitate when it is ¢ooled rapidly than when it is cooled slowly. Rupid cooling gives smaller particles and the air-cushion is larger relatively tg the mass; consequently precipitation is more difficult. Schuster} studied the disruptive discharge through gases and found an apparent diminution of dicleetrie strength with diminu- tion of pressure. Since no sufficient decrease in inductive capac- ity could be observed in the mass of the gus, he assumed that Inyer in. cect with the electrode there was a condensed surface of gas having a large inductive capacity. Sehuster pointed out that some |of the most puzzling facts of the disruptive dis- charge admit of explanation if we once admit the possibility of such a contact layer, diminishing in density with deereasing gas pressure. If this layer of adsorbed gas offers an increased re- sistance to the passage of an electrical discharge, it follows, from ' Phil. Trahs., 160, 337 (1870). * See also Eunenuenc: Die Bodenkolloide, 226 (1915). 3 Comptes rendus, 94, 1187 (1882). 4Bor. deutkch,, chem. Ges., 34, 4081 (1901). ® Phil. Mag. (6) 29, 197 (1880). © 2010 Forgotten Books www.forgottenbooks. orgADSORPTION OF GAS OR VAPOR BY SOLID 23 the Theorem of LeChatelier, that an clectrical stress will tend to remove the film of/adsorbed gas, This enables us to account for many apparently to remove active and will therefore alternating curren mrelated facts. Electrical waves will tend xygen or active hydrogen from an electrode leut down the over-voltage.! Superposing an on a direct current also decreases the over- voltage, making other reactions possible? The experiments of Margules* and Ri ert on the dissolving of platinum find their explanation in the cutting down of the over-voltage.6 With direct current there is oxidation to a higher anc insoluble stage. With alternating or none of the ins rrent the over-voltage is decreased and little Iuble compound is formed. The clectrolytic detector, the crystal detector, and the coherer, as used in wire- less telegraphy, sec plete elimination m to owe their action to the partial or eom- pf an air film by means of electrical stress. The essential difference between the coherer and the detector is that coalescence t: in the latter. Tt is interesting platinum only whe} kes place readily in the former case and not re note that Lenard® found that mercury wets a.current is flowing. At other times therc is evidently an air film. It has been elaimed by Allen’ that the photo-electrie fatigue of metals is duc to a change in the surface film or gas or in Ié cannot. be: due physical change su: change in the for or to a disintegrati by light (Ramsay the gas included in the metal (Ilallwachs). jto a chemieal change such as oxidation; toa h as roughening of the surface; to an electrical ation of an electrical double layer (Lenard); in of the meta] due to the expulsion of clectrons and Spencer). The difference in the results ‘Rormmonp: Drude’s Ann. 15, 193 (1904); Benxewirz: Zeit. phys. Chem., 72, 223 (1910). ? ARCHIBALD and v x Warrensera: Zeit. Elektrochemie, 17, 812 (1911); Rerruiyann: Ibid., 90, 261 (1914); Guosu: Jour. Am. Chem. Soe., 37, 33 (1915); Srupanory: Chem, Abstracts, 10, 2431 (1916). * Wied. Ann., 65, 6 29; 66, 540 (1898). 4Zeit. phys, Cheml, 44, 81, Zeit. Elektroehemie, 9, 235 (1903); 11, 10, 661 (1905); Hamer: * Revruinger: Zeit] ® Wied. Ann., 30, 2 Heit anarg. Chem., 51, 365 (1906). Elcktrochomic, 20, 261 (1914). 2 (1887). Phil. Mag, (6) 20] 564 (1910); cf. Lewany: Drude’s Ann., 8, 196 (1902); T2, 490 (1903). © 2010 Forgotten Books www.forgottenbooks. org24 APPLIED COLLOID CHEMISTRY obtained by Allen may be duc to the fact that Allen worked at atmospheric pressure, while Robinson’s measurements were made on electrodes at a high vacuum.* In eases of marked adsorption of gascs it is interesting to determine what is the probable density of the adsorbed gas. Mitseherlich? ealeulated that, when carbon dioxide at atmos- pherie pressure and 12° is adsorbed by bexwood chareoal,| the carbon dioxide occupies only one fifty-sixth of its original volume. Since this is a lesser volume than the same amount of carbon dioxide can occupy as a gas at this temperaturo, it is usually assumed that some of it has been liquefied. It is possible, how- ever, to consider the carbon dioxide as present in the fori lof a highly condensed gas which has not liquefied. It might be inter- esting to study the behavior of carbon dioxide near the critical point in presence of charcoal. The magnitude of the heat of adsorption is an argument in favor of the actual liquefactiqn of the gas. Dewar’ has calculated the apparent density of some gases adsorbed by cocoanut charcoal at low temperatures. /The data in Table X show that the densities are of the same order as those of the liquid gases and are greater in some cases.| At higher temperatures the amount of adsorption would be smaller and the apparent condensation less. Taste X.—Dsnsity or Gasns Apsorpep py Crearncoan Density in grams per cubic centimeter. Trempesature | Bena Gas adsorbed TRorps” | Raped’ | Tiguctfed tion ‘en3 ead Carbon dioxide..... | +15 0.70 Oxygen.. 183 1.33 Nitrogen...... 193, 1.00 Hydrogen... = 198 0.06 Hydrogen. .. | =210 0.08 Hydrogen... . ; 252 ou | Vielium. | 958 0.17 (0. 122) } Phil, Mag. (6) 28, 255 (1919). 2 Sitmungsher, Akad, Wiss, Berlin, 1841, 376, * Proc. Ruy. Inst. 18, 438 (1806 © 2010 Forgotten Books www.forgottenbooks. orgADSORPTION OF GAS O& VAPOR BY| It is to be noticed that the vapor pressure of a SOLID 25 film of adsorbed gas in an apparently liquefied state stands in no relation to the vapor pressure of a mass of the liquefied gas. The phase rule generalization that the vapor pressure is constant for the system, Jiquid and vapor at constant temperature, holds good explicitly only in case the disturbing effects clue to gravity, clistortion of the solid masses, and capillary tensions are soon as a liquid film becomes thin enough so 1] eliminated. So at the liquid no longer has the properties of matter in mass, the vapor pressure need not remain constant. When we have an| or liquefied gas, the vapor pressure will vary als of the adsorbing agent. The lowering of the ¥ shown by the fact that oatimeal,! previously dri perature, has been used instead of sulphuric acit freezing of water under the recciver of an air-puny adsorbed liquid with the nature apo pressure is ied at high tem- to produce the ip. L. J. Briggs? showed that the weight of the water film condensed on the sur- face of quartz at 30° in an atmosphere withi onc pereent of saturation is 26.6 mg per square meter as deterjnined by drying h at 110°. This corresponds to a calculated thicls film of 26.64 assuming the density of the form and equal to unity. Neither assumpti accurate, ess of the water film to be uni- n is absolutcly Since the amount of adsorption inereases rapidly with falling tempcrature, adsorption must be accompanic by a marked evolution of heat. In Table XI the data not brackctted are by Favre.’ Atl the molecular heats of adsorption the corresponding heats of liquefaction. The are higher than bnormaily high values for hydrogen in palladium and platinum cannot be due to dissociation into monatomie hydregen, because aceompanicd by an adsorption of heat. They| part to an oxidation of hydrogen. Masson* eo heat of adsorption of water vapor docs not d from the heat of liquefaction; but Dewar’s d: confirm those of Favre, and we know also that {| 1'fuomson: Phil, Mog. (4) 42, 448 (STD. * Jour. Phys. Chem., 9, G17 (1905). * Ann, Chim, Phys. (5) 1, 209 (1874). 4 Pros. Roy. Soc., 74, 249 (1904), sDewan; Proc, Roy. inst. 18, 183 (1905). that would be imay be due in siders that the iffer materially ta,5 Table XII, here is always a © 2010 Forgotten Books www.forgottenbooks. org26 APPLIED COLLOID CHEMISTRY heat effect when porous solids are wetted by liquids.! | This is probably due to an actual increase in the density of the adsorbed liquid. Tanie XL—Moxzcunar Hears or Apsonerion axp or Liguesavrion or GASES 7 Aasobine sees jam | tien | Haart, Platinum.............--.00...] He 46,200 (240) Palladium. . Hy 13,000 (240) Chareoal....... NH: | 5,900— 8,500] (5,000) Chareoal....... CO, | 6,800— 7,800) 250 Charcoal N.O | 7,100— 7,700) 4,400 Chareoal... 80, 10,000—10, 900; 5,600 Chareoal... HCl | 9,200—10,200] (B,600) Chareoal. HBr | 15,200—15,800| (4,000) Chareoal. .. | HT 21,000-—28,000} (4,400) Melsens? found that when 25 ce of different liquids were added to 10 grams of freshly ignited wood charcoal thete was a rise of temperature of several degrees with ether, aleohol, and Taste XIL—Mouucunar Heats or Ligvsraction anp ApsoRPTION OF Gases Charcoal as adsorbing agent at — 185° (Dewar). Gas ecto, | Bayete, Hydrogen 1600 BBs Nitrogen... 3686 1372 Argon... . 3036 Oxygen... 3744 1664 Carbon manoxide 3416 carbon bisulphide. When 97 grams of bromine were atlded to 11 grams of charcoal the rise of temperature was about 30°. Since a sudden compression of ten atmospheres raises the tem- ‘CE Pournuer: Aon. Chim, Phys, (2) 20, 141 (1822); Cuarruts: Wied. Ana. 19, 21 (1883); Mantive: Phil. Mag. (5) 47, 329 (1889); 50, 618 (1909); (6) 15, 595 (1903); Parks: Thid. (6) 4, 240 (1902); 5, 517 (1903), * Ann, Chim, Phys. (5) 3, 522 (1874). © 2010 Forgotten Books www.forgottenbooks. orgADSORPTIO; perature of water onl; rise of lemperature o! corresponds to a pressure of 893 atmospheres. the same way he drew is 3100 atanospheres v OF GAS OR VAPOR BY SOLID 27 1/77 of a degree he concluded that the 1.16° when charcoal is wetted by water Calculating in the conclusion that the foree of adsorption ‘or bromine, 13,090 for carbon bisulphide, 4620 for ether and 3080 for aleohol. Gaudechon? obtain liquids, with wood chat with the temperature, gases and vapors do received any speeial al Tavis XIIT.—Hear d the data given in Table XIII for different coal. Since the heat of liquefaction varies it is probable that the heat of adsorption of also; but this point seerns not to have tention. Evorution on Wetting Woop Cuarcoan Gran calories per gram charcoal. cat | al Water...........00...f 8.9 | Acetone. 8.6 Methyl alcohol 11.5 | Chloroform..........} 2.3 Ethyl aleohol. . 6.9 | Ether. 1.2 Propyl aleohol. . 5.6 | Benzene. 42 Amylaleohol...........) 3.7 15 Formic acid............) 12.0 4.0 Acetic acids... 6.0 o.4 Lamb and Coolidge? find that eurves, which approximate closely to straight lin tion of the vapors of s| against the amounts al of adsorption and the net heat of adsorption s, are obtained when the heats of adsorp- me organic liquids by charcoal are plotted sorbed. The difference between the heat heat of vaporization is called by them the and is practieally constant for the different liquids studied, when referred to equal volumes of adsorbed liquid. Assuming th: compression, the attr: t this net heat of adsorption is a heat of eting force is estimated to be about 37,000 atmospheres when one cubic centimeter of liquid is adsorbed by ten grams of charcoal The action of wat 1 Comptes rendus, 187, 2 Jour. Am. Chem. Sie, r vapor on cottdn has been studied by 209 (1913). 42, 1146 (1920). © 2010 Forgotten Books www. forgottenbooks. org28 APPLIED COLLOID CHEMISTRY Beadle! and by Masson? If the bulb of a pthermometer be covered with carefully dried cotton wool, and if the butb be then dipped ins beaker or water at the same temperature, the thermom- eter will rise 8°-12° or even more. The relatively large amount of air which is always entangled in the cottom wool does not escape during or after immersion, and the fibers present a glisten- itg appearance under water, which suggest that they are not wetted completely. Medieated or absorbent cotton differs from the ordinary, nearly pure, material in that the former has been freed from traces of natural cotton wax by treatment with solvents. When absorbent cotton is dipped jinto water, the rise in temperature is less than in the previous case even though more water is taken up by the cotton. In the case of the nearly pure cotton wool, the water evidently distills across the air space, while there is a certain amount of direct wetting with the absorbent cotton. There should therefore be 4 marked evolu- tion of heat if cotton is placed in saturated water vapor and the two cottons should behave exactly alike. Both these predictions were confirmed experimentally. Masson obtained similar re- sults when guncotton or glass wool was exposed to saturated water vapor or cotton to the vapor of absolutejaleohol; but the heat, effects were much smaller in these instanqes owing to the lesser adsorption. LB. Loeb? finds that the adsorption of mcthy] alcohol vapor by 0.41g platinum black causes a rise of temperature of about 0.36° when there is no oxidation. The cffcet of traces of impurity on the adsorption is shown in some experiments by Berliner.t| His purified palladium foil adsorbed about 860 volumes of hydrogen. If allowed to stand in 2 vacuum for an hour, it then adsorbed practicglly no hydrogen. Tf left for an hour or two in the air, the same jthing happened. The disturbing factor is apparently a trace of| grease, because water did not wet the soiled palladium. Similar results were obtained with platinum. 1 Naturo, 49, 457 (1884); Chem. News, 71, 1 (1895); 78, 180 (1896). * Proc. Roy. Soc., 74, 230 (1904); Masson and Rrctarps: Ibid., 78A, 412 (1906). ® Proe, Nat. Acad. Sci., 6, 107 (1929). 4 Wied. Ann., 35, 208 (1585), © 2010 Forgotten Books www.forgottenbooks. orgADSGRPTION OF GAS OR VAPOR BY SOLID 2 Tur Apsonption IsoTHERM So far we have only coramitied ourselves to the qualitative statement that the amount of adsorption increases with inereas of pressure. Tt is now advisable to consider the quantitativ} side. Dewar! has made some measurements with hydroge| at varying pressures in charcoal at —185°. The results are given in Table NIV. Dewar says in regard to them that th amount adsorbed is seen to increase with the pressure to 10 atmog- pheres, after which the adsorption in the pores of the charcodl scoms to be independent of the pressure. At the temperature of liquid air this sample of charcoal (6.7 g) would not adsorb move than about one liter of hydrogen even when the pressure was raised from 10 to 25 atmospheres. It appears that Dewar considers the decrease from 156 ce to 138 ce as due to experl- mental error for he says distinctly that the adsorption had come to a limit. Since that time a number of careful investigatiorjs have been made on the quantitative variation of the adsorption with the pressure.? Tauts XIV.—Hyprocun Apsorben py Cuarcoan at —186 Atm. ] eefaram Atm. ea/gram 1 92 15 149 5 138 20 145, 10 166 25 £33 If we plot the amounts of adsorbed gas against the pressures, we vei the so-called adsorption isotherm, a smooth curve conca to the pressure axis. Trouton* obtained a curve with the oppd- site flexure for the adsorption of water by flannel; but Massor|* 1 Proc. Roy. Inst., 18, 437 (1906). 2Travrne: Proc. Roy, Soc., 78A, 9 (1908); Davis: Jour. Chent. Soc., 94, 1066 (1907); Geopes: Drude’s Ann., 29, 797, (1907); Borne: Jour. Phyp. Chem., 12, 481 (1908); Phil. Mag. (0) 17, 377 (1909); McBain: th 2 18, 918 (1909); Zeit. phys. Chem., 68, 471 (1909); Hommeay: Ibid, 7 130, 687 (1910); Trrorw: Ibid., 74, 611 (1910); Prurte any Maauia: Gaz! , 40 I, 569 (1910). Roy. Sve., 77A, 292 (1905). , TBA, 9 (1906), chim, 3 Pre “Thid.. © 2010 Forgotten Books www.forgottenbooks. org80 APPI obtained normal cu obtained normal cury so that Trouton’s rq 70 60 50 & 3. PRESSURE IN CENTIMETERS nN Me 8 3 FED COLLOID CHEMISPRY rves for water and cotton, and Travers! es for wool and cotton with water vapor, esulis are apparently duc to experimental go" lo “797 error. Trouton? als: adsorption of water alkali dissolved from| 2 3 4 5 Me ADSORBED "PER GRAM CHARCOAL Fig. 1. obtained an abnormal type of curve for the vapor by glass; but it seems probuble that the glass has been a disturbing factor. 1 Proc. Roy. Soc., T9A, 204 (1906). *Thid., 79A, 383 (190 ). © 2010 Forgotten Books www.forgottenbooks. orgADSORPTION OF GAS OR VAPOR BY SOLID 3h If the gas js adsorbed but slightly, the curve may scem practi- cally a straight line over the ordinary pressure ranges. ‘This is shown very ¢learly in the curves for hydrogen in chareoal Vig. 1 as determined by Titofl. If the gas is adsorbed strongly, the isotherm bends around so as to run nearly parallel with the pressure axis, because then a marked increase in pressure causes 175" | [rea [* 25 20 = 30" % & 5 5644), x 8 é 8 g 201 —— fy s i & 50} q q lo 20 20 60 20 700 00 CO, ADSURBED PER GRAM CHARCOAL Fis. 2. only « relatively slight incrense in adsorption. These two ex- tromes can be roalized very well wilh ammonia and charcoal? at 175° and|—64°, Fig. 2. In Table XV are given Titoft’s data for the adsotption of ammonia by charcoal at 0° and at 151.5°. Under axjay jis given the mean increase in adsorption with increase of pressure between each two consecutive observations. ' Zeit. phys.|Chem., T4, 641 (1910). 2 Rucuanpsdn: Jour. Am, Chem, Soe., 38, 1828 (1917). © 2010 Forgotten Books www.forgottenbooks. org32 APPLIED COLLOID CHEMISTRY ‘At 0° the values drop from 92 to 3, a ratio of over 30:1, while at 151.5°, the drop is only from 51 to 11, a ratio of less than 5:1. Tf wel plot the logarithms of the amounts of adsorbed gas (fants XV.—Apsorption or Ammonia BY CuarcoaL ‘Temperature O° Temperature 151.5° Pressure | Adsorption Ax/ay Pressure | Adgorption Ax/ay in mm inee ecfmm in mm ince ees 2.9 bad bese ; 0.8 28.3 30,2 0.92 1.0 0.051 78.7 60.4 0.65 2.1 0.021 161.0 90.3, 0.36 ad 0.018 319.2 116.7 0.16 5.6 0.018 490.0 |] 127.0 0.07 72 0.012 636.4 132.4 0.04 8.0 0.012 746.7 135.9 0.03, 10.5 0.081 against |the logarithms of tlie pressures, we get a curve which approximates a straight line, especially if the gas is not adsarhed too mugh, This shows thal the data can be represented approxi- mately by an equation! of the form (x/m)" = kp, where a is the Tapia XVI.—Apsorrtion o¥ Cannon Dioxrpn BY Crarcoan Formula x 17/p = 0.0602. CO: adsorbed per ec chareoat. lessure inmm Hg. Temp, SL". P x found | xeale | > | xfound | x eale, 41.5 ve | oar 453 65 5 64 120. 2.9 3.1 534 T1007 194. 4.0 4.0 602 76 1 76 276. 47 4.9 G78 8.3 8.2 340. 5.4 5.5 69s 8.6 8.3 405. 5.9 5.0 703 8.9 8.4 amount) of gas adsorbed and mm the amount of the adsorbing solid, yale p is the pressure and # and n are constants Lo be determined experimentally for each temperature. The expo- ' Cheipists are in the habit of culling this an exponential formula whieh is not ecorrqct in the strict aathernatics! sense; but which is justified by usage. © 2010 Forgotten Books www.forgottenbooks. orgADSORPTION OF GAS OR VAPOR BY SOLID nential factor, n, is usually not an integer and its physic canee is unknown.! In Table XVI are given some 33 1 signifi- data by Geddes? on the adsorption of CO. by charcoal, The formula enables us to calculate the adsorption with a moderate would have looked better, but there seems no adv: degree of ntage in accuracy. Of course data could have been picked co which doing this. The formula cannot possibly represent for pressures at which the curve runs nearly parallel to he facts the pres- sure axis, and the experiments of Richardson* on the alsorption vag i i | AOSORFTION Fis. 3. of ammonia by charcoal makes it probable that the] never describes the facts accurately over any wide pressures. For the present it should be considered 2s able interpolation formula, though it may possibly bel same category as the simple gas Inw. The fact that we gel a smooth curve when plotting direct, against adsorption shows that no definite coal formed. In Fig. 3 the pressure is plotted along th axis and the amount of gas condensed on or by uni equation range of ln service ng in the pressure pound is vertical mass is * For a slightly different formulation, see Wittrams: Trans, Faraday Soe., 10, 167 (1914; Proc. Roy. Soc., Edinburgh, 391, 48 (1919). 2 Drude’s Ann., 29, 797 (1909). 3 Jour, Am. Chem:Soe. 38.1828 (1917), 3 © 2010 Forgotten Books www. forgottenbooks. org[34 APPLIED COLLOID CIEMISTRY plotted along the horizontal axis. The typical adsorption iso- therm is represented by the curve OH, while OABCDE is the urve (not to scale) for the taking up of water by sodium sul- ate. Along OA the solid phase is anhydrous sodium sul- hate. Along AB the pressure remains constant because three phases are present; NasSO., Na2SO,..1091.0, and water vapor. Along BG the pressures change without any more water being faken up and consequently there are only two phases, water apor and the compound Na,80,.10H.O. The composition f the compound is given by F, the point at which the prolonga- tion of CB euts the axis of abseissas. Along CD the phases are NaSO.10H.O, saturated solution and vapor, so the pressure remains constant, while unsaturated solution and vapor coexist nlong the curve DE. Many curves of this type have been de- ermined by Browne! and others in his laboratory for the am- monia compounds. The curve OH is clearly not of this type and epresents either 2 continuous series of solid solutions or an ad- orption, The equilibrium is usually reached fairly rapidly, which is an argument against the existence of a solid solution hough by no means 4 conclusive one. More convincing is the ‘act that the amount of adsorption by charcoal varies with the tructure? and the extent of surface. The change produced by grinding charcoai? is only a slight one, because the surface of the inground charcoal is so enormous. Lagergren‘ estimates that ne gram of charcoal has a surface of four square meters and is omposed of about 1.4 billion particles. Lamb, Wilson and haney’ consider that one eubic centimeter of active war charcoal has a surface of about 1000 square meters (density about 0.4). While the experiments on the taking up of gases by charcoal how fairly conclusively that surface phcnomena are the iin- ortant ones, there is always the possibility that a solid solution may also be formed to some extent. MeBain® considers that 1 See Brownn and Hounnuan: Jour, Am, Chem. Soe., 35, 649 (1913). * Prove and Macria: Gazz. chim, ital, 401, 569 (1010). *Cnarruis: Wied. Ann., 12, 164 (1881). Ci. also Gorwrtscn: Zeit, Kolloidchemie, 11, 17 (1912). 4 See Van BExagsen: Die Absorption, 410 (1910). * Jour, Ind. Eng. Chem., 11, 420 (1919). ® Phil. Mag. (6) 18, 916; Zcit, phys. Chem., 68, 471 (1909). © 2010 Forgotten Books www.forgottenbooks. orgADSORPTION OF GAS OR VAPOR BY over 13 percent of the hydrogen taken up by ¢ at the temperature of liquid air is present as On the other hand Titoff? believes that the am dissolved in the ehareoal has been over-cstimay The truth of the matter is that we have no definj will enable us to distinguish aceurately in all ea} solution and adsorption. In the case of cellulo: SOLID 38 peoanut charcoal solid solution.! unt of hydrogen ed by McBain. e criterion which es between solid e and of gelatine it is quite possible that some water is actually dissolved. Until we know more about the subject it is safer to t! ease as chiefly one of adsorption. teat any doubtful On the other hand, the two special cases of metals and rubber with gases call for some special comment. As: ence of pores jn platinum or palladium foil, o1 the selective diffusion of hydrogen by postulati the pores and subsequent diffusion. At high adsorption would be much less, and it is diffie increased rate of selective diffusion. It is simp the diffusion of hydrogen through platinum by| some of the hydrogen actually dissolves in the pl: case the solubility should be independent of th ture of the platinum. This seems to be true wit for platinum and within wide limits for palla| probable that platinum can dissolve several vol runing the exist- e can account for Ing adsorption in emperatures the It, to explain the ler to account for postulating that tinum. In that e physical struc- bin narrow limits jum. It seems mes of hydrogen at ordinary temperatures, and palladium nearly cight hundred volumes. The bulk of the hundred volumes of are taken up by platinum black’ must be adsor! must be true of the nearly 3000 volumes take: platinum.® This is apparently the conclusion Edgar, and Firth.7 If platinum and palladiun| Cf. Travers: Proc. Roy. Soc. TBA, 9 (1906), 2 Zoit, phys. Chem., 74, 641 (1910). hydrogen which ed, and the samo up by colloidal reached by Holt, dissolve hydro- 2Por other discussions, see Masson: Proc. Roy. Sac., 74, 251 (1904); Davis: Jour, Chem. Soe. 91, 1066 (1907); Geppss: Drude’s Ann, 29, 797 (1908); Wouter, Puoppemann and Womusr: Zeit. phys. Chem., 62, 670 (1908); Horna: Ibid., 74, 139, 687 (1910). 4 Cf. Boss: Zeit. phys. Chem., 34, 708 (1900). 5 Ramsay, Monp and Sutexps: Zeit. phys. Chom., 19 (1898), ® Paar and Gzrum: Ber, deutsch, chem. Ges., 41, 80} 7 Zeit. phys. Chem., 82, 813 (1913). 40 (1896); 26, 657 1908}. © 2010 Forgotten Books www.forgottenbooks. org36 APPLIED COLLOID CHEMISTRY goo to some extent, the passage of carbon monoxide through heated iron cannot be attributed to adsorption. At present it is not possible to say whether an iron earbonyl plays any part in the diffusion or not. In the case of platinum and oxygen Ramsay, Mond, and Shiclds' consider that most of the oxygen taken up forms Pt (Ol), ‘They point out that Thomsen ob- tained an evolution of heat of 17,000 calories for thereaction Pt+0+H,0, while they find 17,600 calorics for the so-called adsprption of sixteen grains of oxygen by platinum. Ih view of the relative hchavior of rubber with water and with pyridine, it is hard to sec how the permeability can be a question primarily of adsorption. 1 think that we must assume that carbon dioxide, pyridine, ete., actually dissolve in rubber. Tapie XVIL—Apsorrtion or Carbon Dioxion ny Bsoop Cuarcoan Formulax/p = 0.00024, x) = taillimols COs per gram charcoal. P = partial pressure in mm Hy, Tpmperature 20°, »fo= [| fo» | = | * 613.1 0.4461 0.00024 837.7 0.0855 0.00025 oud 0.124 9.00023 $25.5. 0.0808 0,00025 a. 0.1320 0,00022 312.2 0.0706 0, 00023 453.1 0.1014 0.90022 229 0.0560 0.00024 437.2 0. 2036 0.00025 221,2 0.0523 0.00023 485.2 0.1063 0.00024 176. 0.0452 0.00026 348.5 0.0344 0.00024 \ 170.2 0.0451 000026 330. 9.088 0.00026 | mean | 0.00024 While the equation x/in = kpis a special case of the equation (x/m)" = kp, where n= 1, and therefore nay hold even in casts of adsorption, it is also the simplest case of Henry’s law for the| solubility of gases in liquids. Reychler? found that the amount of carbon dioxide taken up by blood charcoal was pro- portional to the partial pressure of the carbon dioxide in the vapor phase. The data are given in Table XVII. It docs not i Tbid., 25, 684 (1898). ? Van Bemmelen Gedenkbook, 55 (1910), © 2010 Forgotten Books www.forgottenbooks. orgADSORPTION OF secm probable that CO. GAS OR VAPOR BY SOLID 37 dissolves in carbon, and TI prefer to consider this a case of adsorption where the exponential factor happens to be unity. T is view is confirmed by the fact that ‘hy Geddes obtained very different relations for the adsorption of CO, by charcoal at 31° (Ti Reychiler also found tha up by rubber was propor range of pressures. This cirbon dioxide in rubber. The concentration-press dium! has two ascending is nearly but not quite, pq not known to what extent adsorption. While many people are let it go at that, attempts tion cither through the fq pounds. Rhead and Wh oxygen by earbon involves| which breaks up into carb heated. Haber? points o1 nary solid crystalline salts and one cation form a mol but that one anion is pr cations. Unless the outer ble XVI. the amount of carbon dioxide taken ional to the pressure over a narrow may well be a case of solution of ure curve for hydrogen and palla- hanches connected by a branch which vallel to the concentration axis. It is e peculiarities of this curve arc dueto willing to speak of adsorption and to ave been made to account. for adsorp- rmation of known or unknown com- leeler? consider that the fixation of the formation of a compound, C.0,, m dioxide and carbon monoxide when ¢ that, according to Bragg, the ordi- are not systems in which one anion cule which is separated from the next; bably bound to all the surrounding ayer of a crystal differs fundamentally from the inner portions, th erystal similar to those ac] next layer. If we call th sort, it is possible that ads« tion of these valences. Langmuir! as a result of carbon and other filamen of 0.004-0.007 mm. La > Horrsema: Zeit. phys. Cl Suretps: Thid., 19, 25 (1896); 82, 513 (1913). 2 Jour. Chem. Soe. 103, 462 # Jour. Soe. Chem, Tnd., 38, + Jour. Am. Chem. Soé., 37, re must be forces at the surface of the ting between the outer layer and the se forces chemical valences of some rption is due essentially to the satura- hese ideas have been developed by nis experiments on electrically heated Is in presence of oxygen at pressures muir eonsiders that any erystal or em, 17, 1 (1895); Ramsay, Monn, and our, Epear and Fira; Jour, Chem. Soc., (1913), 0; Zeit. Wiektrochemie, 20, 521 (1914). 139 (1915); 38; 1145, 2221 (1916). © 2010 Forgotten Books www. forgottenbooks. org38 APPLIED COLLOEM) CHEMISTRY any mass of liquid forms a giant molecule, and t: gas forms a compound with the outer layer, the at an adsorbed hickness of the reacting gas film being rarely over one or two molecules thick. Looking at the subject from a kinetic point of an equation of the form where Q is the amount adsorbed at the pressy and c are constants. There sre iwo independent questions involved iew he deduces re p, and a, & in Langmuir’s hypothesis, namely whether the maximum adgorption film is only one or two molecules thick and whether thi compound with the adsorbing agent. The firs and the second be wrong. Langmuir claims th: film never exeeeds tivo molecules in thickness for| though he is apparently willing to concede a gi for porous substances. There is no question but tion film is very thin. Mitscherlich! calculates about 50upn for carbon dioxide adsorbed by ch: film of water round each particle of clay? is usuall, of the same thickness, while L. J. Briggs* cstim: for the film of water on quartz. It is difftcult 4 these points because one does not know the su degree of accuracy; but the evidence is in favo contention. When it comes to tho question of whether is layer forms a ib may be true +, the adsorbed planc surfaces, eater thickness hat the adsorp- a thickness of reoal, and the assumed to be ics about 27 p46 be certain on inface with any of Langmuir’s ompounds are formed or not, it must be remembered that Langmuir uses the word molecule in a new sense. He considers thai all that in them is constitute one vast molecule ing a fish isa chemical reaction because it breaks This may be perfectly true; but the usefulness of made clear. For the present, it seems much wi the occans and nd that eateh- tp the molecule. it has not been er to say that one substance adsorbs another selectively, m¢aning that the concentration at the surface of the phase has increased. When- ever there is no proof that, a compound is forme} 1 Sirzunasner: Akad. Wiss. Berlin, 1841, 379. 2 Cf, Davis: Trans, Am. Ceramic Soc., 16, 69 (1913). ° Jour. Phys. Chom., 9, 617 (1905). of the type at © 2010 Forgotten Books www.forgottenbooks. orgADSORPTION OF GAS OR V APO) present recognized by chemists, it is safc existence of compounds. When the time tinct advantage to distinguish an entirely 1 an indefinite chemical compound, that cai confusion will arise whenever & man uses 4 his listeners in another. It is quite probal study of contact catalysis may force us view or some modification of it; but it wi gather in a lot of the loose ends. In some cascs compounds are undoul when platinum biack takes up oxygen, a is certainly present as oxide. On the ot: probable that it would be so difficult to mal direct if the chlorine, which is adsorbed R BY SOLID 39 ir not to postulate the comes that it is a dis- ew type of compound, be done; but hopeless word in one sense and ble that 2 more careful to adopt Langmuir’s then be necessary to tedly formed. Thus portion of the oxygen er hand, it seems im- ¢ carbon tetrachloride 'y ehareoal and there- by made active,' consisted of a normal compound of carbon and chlorine. While the oxidizing action of pl a platinum oxide, this cannot be true in th oxygen. Calvert? showed that oxygen will oxidize ethyl alcohol to acetic acid ai dioxide and water, reactions which certail any known oxide of carbon. It also se¢ postulate that the noble gases form definit with charcoal. Years ago Angus Smith® ignored the v: with the pressure and concluded that: at| charcoal adsorbed gases in volumes whi the volumes of hydrogen adsorbed. His fi: 1; oxygen, 7.99; carbon monoxide, 6.03; mothane, 10.01; nitrous oxide, 12.90; su nitrogen, 4.66. Smith lays stress on the carbon dioxide and the 10 for methane ¢: +16 and 6 + 4 respectively, though it is di] proves. In order to make the value for ni Smith points out that 14 x 4.66 = (14)} tions are only of historical interest now. 1 Damorszau: Comptes rendus, 73, 80 (1876). 2 Jour, Chem, Soe., 20, 293 (1867). iatinum may be due to ¢ case of charcoal and dsorbed by charcoal d ethylene to carbon mly cannot be due to fms unsatisfactory to chemical com pounds riation of adsorption atmospheric pressure ih were muitiples of sures were: hydrogen, arbon dioxide, 22.05; jphur dioxide, 36.95; fact that the 22 for te be considered as 6 cult to see what this rogen seem plausible, ; but these caleula- Chem. News, 18, 21 (1868}; Proc. Roy. Sve., 28, 322 (1879). © 2010 Fo gotten Books www. forgottenbooks. org40 APPLIED CO. Creme Since reaction velocity is p} difference of chemical pote! the chemical resistance, we either by increasing the diff decreasing the chcinical resi tion due to adsorption at th cause an increase in reacti catalytic action which the ¢ LOLD CHEMISTRY 1 REACTIONS ‘obably directly proportional to the tial and inversely proportional to can increase the reaction velocity erence of chemical potential or by stance. ‘The increased coneentra- e surface of a solid will necesswily n velocity quite apart from any olid may exert.t In the form of wood ashes, charcoal is often used in outhouses and elsewhere to climinate unpleasant odors. ferous substances and then aj which is adsorbed from the tor filled with powdered woe and which should adsorb an other diseases. This was mask. It is not known whet! coal is due to anything mor of the oxygen. As a matter of fact, the relatively unimportant in Patrick’s silica gel has a surf: an excellent adsorbent, but, catalytic effect exeept in the! be interesting to try this subs of alcohol and acetic acid, b The charcoal adsorbs the odori- jccelerates their oxidation by oxygen ir, Shenstone® invented a respira- id chareoal to be worn in hospitals then destroy germs of cholera and he forerunner of the modern gas er the oxidizing uction of the char- than the inercase in concentration ffect. of concentration scems to be ost of the cases studicd hitherto. co of 2.5 X 10° om* per gram and is o far, it does not have any marked oxidation of nitric oxide. It would tance at 100° with the mixed vapors cause this reaction takes place ata measurable rate in the vapor phase in the absence of any catalytic agent. It is stated that oxy| quite stable under pressures shows that the catalytic acti gen and oxygen must be dus in concentration. The maf platinum and charcoal towar ment in favor of the action On the other hand Hempel’ 1 See, however, Lancauir: Jou 2 Pharm, Jour, 13, 454 (1854). ch. chem, Ges, 23, drogen gas has heen found to be f two thousand atmospheres, which a of platinum on mixtures of hydro- to something more than a change ed differenee in the behavier of 1 oxyhydrogen gas is another argu- lof a catalytic agent being specific. with SQ2 and O2 obtained a yield . Am. Chem, Suc., $8, 2286 (1916). H15 (1810). © 2010 Forgotten Books www. forgottenbooks. orgADSORPTION OF GAS OR VAPGR BY SOLID 4 of 65 percent s without any catalytic agent by working ata pressure of thirty to forty atmospheres. If we have se eclive adsorption of the reactiou products, this will cause a lowering of the chemical potential of the resultantst and will therefore incrcasc the reaction velocity. It may even determine the direction of thereaciion. Alcoliol breaks down into acetaldehyde an into ethylene an| silica? Since ni hydrogen in presence of pulverulent nickel and d water in presence of pulverulent alumina or ckel adsorbs hydrogen strongly and alumina adsorbs water, it seems natural to assume that the selective adsorption is the determining factor.* Whilo this seems very satisfactory, there are certsin points which must not e overlooked. When making ethylene at edge- wood Arsenal during the war, it was found advisable to have a large amount of steam present with the alcohol vapor in order to maketemperature regulationeasier. This undoubtedly decreased the rate of decomposition of the alcohol; but thai difficulty was overcome by wot cult to see how 4 large amount of cause of its stron: very little proba king at a higher temperature. It is very diffi- Jumina can dehydrate aleohol in presence of a water vapor if the reason the alumina acis is be- adsorption of water vapor. Sinee there seems ility of accounting for the various decomposi- tions of the esters on the busis of sclective adsorption of the re- action products, phenomena of ed lines. If changes in it is probable that a complete explanation of the intact catalysis is not to be found along these ithe chemical potential are not the important factors in contac catalysis, the catalytic agent must change the chemical resistanec in some way, and there are two possible ways in which thi is might happen. We may have more effective collisions bobweer existing molecules or we may have a conversion of one or more o: According to 4 1W. C, McC, Le the reacting substances into an active form. ine Kinetic theory the reaction velocity is pro- TS suggests the terms reactants and resultants for react- ing substances and feaction products. ? Teatrprr: Ber. d 36, 1990, 2003, 2 rendus, 136, 738, 92 3 Jounson: Jour, sutsch, chem. Ges., 84,3579 (1901); 36, 1047, 1057, (1902) 4, 2016 (1903); Sasarter and SenperEns: Comptes , 936, 983 (2903). Am. Chem. Soe., 34, 911 (1912)._ + Excetver: Joup. Phys. Chem., 21, 676 (1917)7 © 2010 Forgotten Books www.forgottenbooks. org42 APPLIED COLL portional to the number of coll molecules; but it does not follo every lime they collide. If ale sary on an average before a which would make these collisi the reaction velocity enormous whether there is any evicenc maiter has been studied by Str that a molecule of ozone reacts| of silver oxide; but that a mol with a molecule of eopper oxide before they react, while two m on an average 6 X 10" times be ing on the absolute accuracy oj plenty of margin for an inereasc| 100° if one could produce mor finds that 15 percent of all ox: not over 5 bars striking a tu: with it to form tungstic oxide, at higher temperatures and at the oxygen molecules which st form WO; Sinee there are th: ID CHEMISTRY isions between possibly reacting v at all that two molecules reaet Irge number of collisions is neces- air of molecules react, anything ions more helpful might increase ly. The first question is then of ineffective collisions. This tt! who comes to the conclusion every time it strikes a molecule lecule of active nitrogen collides five hundred times on an average lecules of ozone at 100° collide fore they react. Without insist- these figures there is evidently in reaction velocity with ozone at effective collisions. Langmuir* ger molecules at a pressure of gsten filament at 1770°K react WO;, This cocfficient increases 8300°K about 50 percent of all ike the filament react with it to ree atoms of oxygen in WO; and only two in the oxygen molecule, Langmuir considers that at Icast one-half of the tungsten s with oxygen in some form. Tt is possible that a catalyta| to strike another amidships inst} increase the effectiveness of thd that part at least of the effeet| may be due to some such thing views? of oriented adsorption, al Tf ethyl acctate, for instance, by the methyl group, to anoth| third by the earboxyl group, it ment of the eaptive molecule I different reaction products in the 1 Proc. Roy, Soc,, 87A, 302 (1912), # Jour. Am. Chem. Soe., 35, 105 (1 2Cf, Desus: Jour, Chom, Sec, -53| irface must be covered at 3300°K agent may cause one molecule a of head-on and may thereby collisions. i is not impossible of solvents on reaction veloeity this. If we adopt Langmuir’s I sorts of things become possible. pttaches itself to one adsorbent r by the ethyl group, and to a ight very well be that bombard- y free ones might lead to very three cases. Such a suggestion 13); 38, 2270 (1916). 327°(1888): © 2010 Forgotten Books www. forgottenbooks. orgADSORPTI is of very little valu We do not know as y in one way by nickcll way by titania, nor manner of adsorptio} as to account for the well be that some en iN OF GAS OR VAPOR BY SOLID 43 , however, unless it can be made definite. i whether ethyl acetate is actually adsorbed in another way by thoria, and in a third ido we know whether the difference in the , assuming it to occur, is of such a nature ifferences in the reaction products. It may irely different hypothesis will prove neces- sary. The general problem of inereasing the effectiveness of molecular collisions i been studied at all. There is one speci one of the factors of distinctly an important one which has not ] case in which we can apparently identify hemical resistance. Buchbéck? studicd the decomposition of carbonyl sulphide and found that the reaction velocity decreased Sinee the reaction pri that the retardation gas bubbles in a mo tion from Rasehig’s the action of hypochl being kept down by more viscous. The NH.Cl + NaOH an NH-;Cl + NH; = NJ 2NH; = 3NH.CI + Instead of more tions of the reacting of one or more of the through the rupture opening up fields of f The conception of| reacting substanees ground admirably ag with it is that it is as hypothesis, though It is necessary to sho and why it happens| sith increasing viscosity of the solution. duets are gases, this suggests the possibility is due to the greater difficulty of forming viscous medium. ‘This receives confirma- work on the preparation of hydrazine,? by lorite on ammonia, the evolution of nitrogen omething like starch to make the solution preliminary reaction is NH, + NaClO = high viscosity promotes the reaction I,HCl as against the one 3NH,Cl + 2 fective collisions between unchanged por- molectles we may have a partial conversion reacting substances into active forms cither of normal valences or of contra-valences, ree as Baly® puts it. Baly that a catalytic agent activates the lby opening up fields of force covers the a purely formal statement. The trouble ‘et too vague to be of any value as a working it ig undoubtedly the best starting-point. vy in each particular case just what happens While the conversion of a reacting sub- 1 Zeit. phys. Chem., 28, 123 (1897); 84, 229 (1900). 2 Henpurson: Cataly, 3 Jour, Chem. Soe., 104 Sis in Industrial Chemistry, 60 (1919). Ht, 1469, 1475 (1922). © 2010 Forgotten Books www. forgottenbooks. org44 APPLIED COLLOID CHEMISTRY stance into an active form may very well account for the effect. of the solvent on reaction velocity in homogencous systcms, it must|be shown what active form is produced and why one sol- vent |produces more of it than another. Activation may lead to the formation of intermediate compounds or it may not; but we have got to get down to more definiteness in all the cases of contact catalysis. It is often assumed that definite intermediate comppunds are formed and this is ccrtainly truce in some cascs. In th catalysis of hydrogen peroxide by mercury, the interme- diate] formation of mereuric peroxide can be detected by the cye because there is an intermittent formation of a film, which then |breaks down, only to form again.t The formation of graphite is nsually preceded by the formation of a carbide. The conversion of acetic acid into acctone? by passing the vapor over heated barium carbonate presumably invelves the intermediate formation of barium acetate, though one cannot ear-mark the carbon dioxide and so cannot be absolutely certain that the barium carbonate is continually decomposed and regenerated. In the Deacon chlorine process, where a mixture of hydrochloric acid and pxygen is passed over heated eupric chloride, Hurter? assumes the existence of an intermediate compound. People ave not agreed, however, whether the intermediate compound is euprgus chloride, cupric oxychloride, or both. The extreme sensitiveness of this reaction to poisons raises a question whether an intermediate compound really is formed. In the catalytic oxidation of carbon monoxide, it is usually believed that there is alttrnate reduction and oxidation of the oxides which act as catalytie agents. Sabatier* helieves that the catalytie action of alumina on alcohpl is due to the intermediate formation of an instable com- pound of alumina and water. - On the other hand, Henderson® assumes the intermcdiate formation of aluminun ethylate. Neither one offers any experimental evidence in support of his 1 BaeniG and von AntRoport: Zeit. Blektrochemie, 12, 581 (1906); vox Awrnovorr: Jour, prakt, Chem, (2) 77, 273 (1908). @Sqima: Jour, Am, Chem, Soc., 17, 187 (1895). 4 Jor. Soc. Chem. Ind., 2, 106 (1883). + Die Katalyse in der organischen Chemie, 240 (1914), 5 Ctalysis in Industrial Chemistry, 4 41919) © 2010 Forgotten Books www.forgottenbooks. orgADSORPTION OF GAS OR V belief, and neither one discusses wh cally as well as alumina. It seems probable that the best ve contact catalysis is to start with the si a good deal and to study the sclectiv Quite apart from any theory we mal questions which ought to be answer these questions have not even been rai know that ethyl alcobol can be dec and hydrogen or into ethylene and ull that we know as yet about these re} nickel the reaction is almost complete CH,CH,OH = CHA We do not know whether the hydrog in two. Jf it comes off in two stages, or CHsCHOH? While it may not which will answer this question, the p} than many which the organic chemis' With pulverulent alumina the real [APOR BY SOLID AS kaolin should act practi- y to solve the problem of le which has been neglected action of catalytic agents. adopt, there arc certain :d experimentally and yet ised in a scrious way. We mposed into acctaldehyde ater but that is practically etions. With pulverulent ly H,O + He nm comes off in one stage or ‘is the first stage CH;CH.0 je easy to devise a method ‘oblein is not more difficult have solved successfully. btion is almost completcly CH,CH,OH = CH.GH, + H,0. Does water split off as such or do hydroxyl or hydrogen? It seems imp! off as such because then it would be intermediate formation of cther. Hf we get the splitting off of ‘obable that water can split \difficult, to account for the he first stage is a splitting off of hydroxyl does the other hydrogen come from the adjacent carbon atom giving ethylene direct or carbon atom, forming a substituted then rearranges to ethylene? One w nickel does with diethy] ether. With nickel we get ihe follawing \loes it come from the same ethylene, CH;CH, which juld also like to know what ecomposition of the esters: CH;CO,CH.CH; = CH;GH.CH; + CO. CH,CO.CH, = CHC HCO.CH.(?) = CH, With thoria the decomposition is qi 2CII;CO.CeH, = CH;,COCH,; + = CH,COCR; + 2CH.CO.CH, = CH,COCHs + 2H COCH, = HCHO. + He + COs t- CO2 ite different: Oo + (CxH,)20 On + CoH.OH + CoH, Oo -+ (CH):0 bOs + (CHs).0 © 2010 Forgotten Books www. forgottenbooks. org46 APPLIED COLLOID CHEMISTRY With titania we have a third set of products: CH;CO.C2Hs = CH;CO:H + C.Ha 2CHsCO2CHs CH;CO.H + CyH, HCO:.CH; = HCO.H + CH: = CO + CH;OH The decompositions are regular and characteristic with cach catalytic agent and the molecules must break or slip at (lifferent points in the different cases; but we certainly ought to kuow what the hypothetical intermediate stages are.t Tako the] ease of inethyl acctate with nickel, for instance. One assumptign might be that we have a methylene dissociation CH;CO.CH; = CHsCO.H + CH, = CHsCHs+ CO, A second assumption is that methyl splits off: CH3CO.CH: = CH:CO2 + CHs = CzHs + CO2 A third assumption might be a splitting off of both mothy] groups: CH.CO:CH; = 2CH: + CO: = Calls + O2. Is any of these what happens and how can we prove it? Also how does the final assumption tie in with the facts that injaqueous solution acetate ion goes to ethane and CO, 2CH;CO, = C2He + 2CO2z and that dry lead tetra-acetate decomposes at about 140° into lead acetate, methyl acetate and carbon dioxide Pb(GH:CQ2)4 = Pb(CHsGO2)2 + CH;CO.CH; + CO: ‘The question also comes up as to the changes in the intermediate stages in case the esters are chlorinated more or less completely. The effcet of the catalytic agent is very marked when it|comes to the preferential oxidation of mixed gases.?. Atlow temppratures, the nature of the catalytic agent may determine which of iwo combustible gases will burn the more rapidly. In prqsence of platinum, copper oxide, or chamotte, hydrogen bums more readily than methane, whereas the reverse is true in bowosilicate glass bulbs at 300°-400°. Depending on conditions, cither hydrogen or carbon monoxide will burn the more |readily.* «This is now being studied experimentally by Prorrssor Houck ADKINS. ? Henny: Phil. Mag., 65, 269 (1826); Bowe: Jour. Chem. |Soc., 81, 535 (1902); 85, 694 (1804); Proc. Roy, Inst., 48, 82 (1008); PHik Trans. 215, 298 (1915). 3 Ripuar: Jour. Chom. Soc., 116, 998 -(1919) © 2010 Forgotten Books www.forgottenbooks. orgADSORPTION OF GAS OR VAPOR At very high temperatures the specific effec: becomes negligible because the reaction will in the gas phase. One very striking characteristic of soli the ease with which they hecome inactive or| the reaction takes plaveinorat the surface, i stence which cuts down the rate at which th reach the catalytic surface! or which preve BY SOLID 47 of the catalylie agent take place so rapidly catalytic agents is are poisoned. Since follows that any sub- reacting substances is them from reach~ ing it, will decrease the reaction velocity pnd may destroy the eatalytie action entirely. Berlincr? has fatty vapors from the air or from the gre: will deerease the adsorption of hydrogen| nearly nine hundred volumes practically has shown that traces of grease destroy 1! platinum on oxyhydrogen gas. De Hempt! shown that carbon monoxide cuts down the gen by palladium, though his method of is very obscure. Lunge snd Harbeck*® fou own that traces of Ise on the stop-cocks by palladium from nothing. Faraday* fe catalytic action of inne? has apparently adsorption of hydro- resenting his results id thet carbon mon- oxide inhibits practically completely the catalytic action of platinum on a mixture of ethylene and h, pointed out that tho hydrides of sulphur, phosphorus, arsenic, and antimony ack ¥ cutting down the catalytic action of plati air with hydrogen or ether. He considered drogen. Schonbein® tellurium, selenium, ery energetically in Inum on mixtures of at the hydride must decompose, giving rise to a solid film. This is not necessary in order to account for the phenomenon; been right in at least one case, for Maxted? } gen sulphide is decomposed by platinum dl] hydrogen and that the platinum then doe gen. Langmuir’ believes that oxygen prey mut he scems to have as found that hydro- ck with evolution of 5S not adsorb tydro- lents the dissociation of hydrogen by a heated tungsten filament because it cuts down the adsorption of the hydrogen. 1 Taxtor: Trans, Am. Electrochem. Soe., 36 (19| * Wied, Ann., 35, 903 (1888). erimental Researches on Electricity, 1, 185 4 Zeit, phys. Chem., 27, 249 (1898). * Zeit. anorg. Chem., 16, 50 (1898). $ Jour, prakt. Chom., 28, 238 (1843). 7 Jour. Chem. Soc., 115.1050 1919). § Jour. Am. Chem. S0c., 38, 2272 (1916). LO). (1839). © 2010 Forgotten Books www.forgottenbooks. org48 APPLIED COLLOID CHEMISTRY Harned!|/has shown that the rate of adsorption? of ehloropicrin bya charcgal which has been clcaned by washing with ehloropicrin is much greater at first than by a charcoal which has not been so cleaned, although the final equilibrium is appsrently about the same ip the two cases. This is analogous to the evaporation of water when covered by an oil film. The oil cuts down the rate of evaporation very much but has practically no effect on the partial] pressure of water at equilibrium. ‘Taylor points out that normally the time of contact between a gas and the solid catalytic agent is extremely small and consequently anything which deertascs the ratc of adsorption will cut down the reaction velocity very mucel. Tt is casy to see that the piling up of reaction products* will cut down the reaction velocity, if they prevent the reacting sub- stances froin coming in contact with the catalytie agent. This has been observed in the contact sulphuric acid process.¢ The explanatio#’ that the decrease in the reaction velocity is due to a decreised adsorption of the reacting substances was first given by Fink® who is the real pioneer in this linc. Although the reaction between carbon monoxide and oxygen is practically irreversible] at ordinary temperature, Henry* recognized that the presence ofthe reaction product might slow up the rate of reaction and he proyed his point by increasing the reaction velocity when he removed the carbon dioxide with caustie potash. Water vapor checks the catalytic dchydration of ether? and of aleohol* and hydrogen cuts down the catalytic dehydrogenation of alcohol. When catalytic poisons are present or are formed during the reaction, the apparent equilibrium may vary with the amount of the catalytic ageni. With only a small amount present, the catalytic agent will be poisoned before the reaction has run very far. In the hydrolysis of ethyl butyrate by enzymes, the reaction + Jour. Am|. Chem. Soc., 48, 372 (1020). * Tay.on:|Trans, Am, Electrochem, Soe., 36 (1919). 8 Bunsen (1857). Quoted by Dracon: Jour. Chom. Soe., 28, 736 (1872). ‘ BovLanper and Koren: Zeit. Llektrochemie, 9 566 (1903); Burt: Zeit. anorg, Chem., 44, 267 (1905). 5 BopensTEIN and Fink! Zeit. phys. Chom., 60, 61 (1907). © Phil, Mag. (3) 9, 324 (1836). 7 Lrarmeert Ber, deutsch. chem. Ges., 37, 2996 (1904). *Encerppe: Jour, Phys, Chem, 21, 676.(1917). © 2010 Forgotten Books www.forgottenbooks. orgAPSORPTION OF GAS OR VAPOR BY SOLID 49 apparently runs|to different end-points, depending on the relative amounts of enzyme.t One may also get abnormal end-points in the hydrolysis of 9 solid, if the product of hydrolysis is also a solid and forms|s film over the reacting substance. With one of the war gases, the amount of hydrochloric acid split off in prescnee of water was practically the same when the amount of water added varied in the ratio of one to four. In other words, an apparent equilibrium was reached at a given concentration of hydrochloric beid in one ease and at one-fourth that eoncen- tration when four times as much water was added. The development of some of the technical contaet processes has been so inipresting that it seems worth while to diseuss a few of them briefly, beginning with the contact sulphuric acid process.* Cowract ScnpHurrc Acio Process In 1831 Phillips discovered that spongy platinum increascs the rate at whieh|sulphur dioxide combines with oxygen according to the equation PSO. + O. = 250;. He obtained a patent for this but could not develop a commercial process. In 1846 Jul- lion patented thle use of platinized asbestos. In 1842 Woéhler and Mahla discovered that the oxides of copper, iron, and chrom- ium aet like platinum. In the Schrocder-Grillo contact material hydrated magnegium sulphate is soaked in a solution of a plati- num salt and then heated in presence of sulphur dioxide. A thin layer of platinum is thus precipitates ou the surface of the porous, dehydrated salt, 0.2-0.3 percent of platinum giving an excellent catalytic agent. Kaietseh found that a practically complete conversion of sulphur dioxide {nto sulphur trioxide could be obtained when sulphur dioxide was diluted with air, the conversion being more nearly complete] the greater the ratio of oxygen to sulphur dioxide. When the experiments were repeated with purified burner gas on a commerciallseale, the contact inaterial soon beeame inert. lé was found that this disastrous result was due to impurities in the burner gases. Even when present in apparently negligible ' Kasrne and Logvensarr: Am. Chesn, Jour., 24, 491 (1900). * Kwrensen: Berdeutsch, chem. Ges., 34, 4069 (1901), * Ripnar and Tafnox: Cutulysis in ‘Theory and Practice, $6 (1919). 4 © 2010 Forgotten Books www.forgottenbooks. org50 PPLIED COLLOID CHEMISTRY be amounts, these impurities play havoc with the catalytic action of the platinum. | Arsenie is the most dangcrous and next mer- cury, while antimony, bismuth, lead, iron, zinc, ete., act in so far as they settle on and actually blanket the contact matcrial. An amount of arsenic equal to 1-2 percent of the platinum fn the contact material will destroy the catalytic action completely. In view of the enormous volumes of gas which are handled, it is easy to sce to what an infinitesimal value the arsenic content must be reduced. By cooling the burner gases slowly and bringing them into intimate contact |with sulphuric acid, it was found possible to obtain a gas mixture which passed all ordinary optical and ehemi- eal tests and which appeared to be pure. When tested on the large scale, if was still found to contain arsenic. The gases had been cooled in long iron tubes and had reacted with these suffi- ciently to give traces of arsine. This difficulty was eliminated by not letting the gases come in contact with the iron. When the roaster furngees were run to maximum eapacity, however, a slight cloud was formed which could not be got rid of and which proved to| consist of unburned swphur. ‘This in itself would have done|/no harm had not the particles of sulphur con- tained some arsenic. It therefore proved necessary to admit. enough air so ag to be sure that the sulphur was burned com- pletely. While no one has shown that the presence of arsenic cuts down the adsorption by platinum, it is quite certain from Berliner’s experiments on palladium and hydrogen! that this must be the case. In American practice the burner gases carry arsenic, lead sulphate, siliccu |tetraflueride, hydrochloric acid, sulphur, and selenium. Reese? calls the first two permanent poisons and the others temporary poisons. When working with platinum on a magnesium sulphate base, it is possible to regenerate the contact, material after it has been poisoned with arsenic by heating with hydrochloric acid. ‘fhe assumption was that the arsenie was volatilized as tha trichloride. Analysis showed, however, that there might be 2-3 percent of arsenic in the regenerated catalyst without its having any apparent effect. It must be that tho ‘Bertier: Wicd. Ann., 35, 804 (1988). 2 Jour, Soc, Chem ‘Ind., 22,351 (1903). ° © 2010 Forgotten Books www.forgottenbooks. orgADSORPTION OF GAS OR VAPOR BY SOLID SL oe arsenic had agglomerated in some way so that it did not co: the platinum. Jn spite of Knietsch’s statement to the contrar it is possible to filter out all the solid poisons. Under ordinary conditions sulphur dioxide and oxygen co: bine very slowly and sulphur trioxide dissociates very slowly i the absence of catalytic agents. In presence of catalytic agen: sulphur trioxide begins to dissociate perceptibly at about 400 and is practically completely dissociated at 1000°. At first sig it would therefore seem that the process should be run below 400°. The time factor is a complicating one, however. With platinun as catalytic agent the reaction begins at about 200°, but relatively slow at that temperature, and under commercial co ditions there is practically no reaction below 400°. It has proved! best technically to work at about 425°-450°, the Increased reaction velocity compensating for the decreased chemical cfficienc: At 425° the conversion is 98 pereent, dropping to 91 percent » 500°. Ferric oxide can be used as a eatalytic agent; but thi reaction velocity is less and consequently it is necessary to wor at » higher temperature with a correspondingly lower chemical efficiency, perhaps 60 percent. Ferric oxide is much less susceptible to arsenic poisoning than is platinum, presumabl. because of the higher temperature at which it acts. Sincere arsenic oxide is itself a catalytic agent when free from iron,? there must be temperatures at which it will have little or nm deleterious action. If one could make a ferric oxide catalys! which would work at as low a temperature as platinum, it is probable that it would be about as sensitive to arsenic poisoning as platinum. It is entirely a question of the way in which thi arsenic precipitates on the surface of the catalytic agent. The heat of reaction for the conversion of sulphur dioxide int sulphur trioxide is given as 22,609 cal per mol of gascous sulphu trioxide. Since this heat is evolved at the surface of the contadh material, it is quite a serious matter to keep the temperature within the proper range. ‘Vhe technical manufacture of sulphui trioxide is therefore very largely an engincering problem and th recent improvements have been chiefly changes in design? so as to give more efficient temperature control. 1 Cl, Beri: Zeit, anozg, Chem.,.44, 267 (1905), * Zeispunc: Trans. Am, Electrochem. Soé., 36 (1919). oa os = 0 © 2010 Forgotten Books www.forgottenbooks. org52 APPLIED COLLOID CHEMISTRY HareGREAVES Saut-cakE Process The Hargreaves and Robinson process! for making salt-eake was establishetl on a practical basis in 1870. The upper tem- perature limit js about 600° owing to the fusion of thesalt. Origi- nally the proecss involved no catalytic agent but consisted simply in the|passage of pyrites gases over suitably prepared salt at 500°-550°, the reaction being 4NaCl t+ 250. + O2 + 2H20 = 2NaSO, + 4HCl In 1886 smal] amounts of iron oxide were added as a catalytic agent. Krutwig? showed that without ferric oxide about 28 percent of the sulphur in pyrites was converted into sodium sulphate after four hours at a red heat. With ferric oxide a 70 percent yield was obtaincd at high temperatures and 90 percent. ai lower ones.) The action is also accelerated by cupric oxide and, sinee 190/, 0.1-1.0 percent of copper or iron salis or both have been aclded to the salt before the latter is moulded, the amount added] depending on the required purity of the product. When the saltteake is to be used in glass works, only a small amount of the| catalytic agent can be added; but the maximum amount is permissible when the salt-cake is intended for the LeBlanc soda} process. Inereasing the amount of catalytic agent increase$ the reaction velocity and lowers the temperature at which the |action starts. In this particular process there is little or no difficulty with the poisoning of the catalytic agent because the oxides are not used over and over again. Deacon Catone Proczss In 1845 Oxland* discovered that chlorine is formed to some extent when a lnixture of hydrochloric acid and oxygen is passed over a heated porous substance. The reaction is 4 HCl + O2 = 2H20 + 2Cl,; put the reaction does not procecd fast enongh to be 2fuonpe: Dictionary of Applied Chomistry, 6, 25 (1913); Joncise: Catalysis and itd Industrial Applications, 82 (1916); Rapeat, and ‘Tartor: Catalysis in Thedry and Practice, 89 (1919). 2 Recueil Trav] chim. Pays-Bas, 16, 173 (1897). 3 TwouPs: Dictionary of Applied Chemistry, 2, 18 (1918); Josra: Catalysis and its| Industrial Applications, 26 (1916); Ries and Tarzor: Catalysis in Thegry aud Practice, 99 (1919). © 2010 Forgotten Books www.forgottenbooks. orgADSORPTION OF GAS OR VAPO practicable commercially. In 1855 Vogel alternately with hydrochloric acid and ox; and Hurter put the process on a succes: passing @ mixture of hydrochloric acid a impregnated with cupric chloride which a Ibis usually assumed that this is not a eas but that the cupric chloride breaks up int chloride which latter combines with 0} oxychloride, CuO.CuCh. to form cuprie chloride, after which the w take place again and again. There is no it is really quile as probable that the o: with the hydrochloric acid,which is what is no cupric chloridepresent. The catalyti to the effect of impurities, such as sulphuy oxide, and arsenic. It is because of this dioxide that the hydrochloric acid from th process cannot be used in the Deacon bad for the reaction. The gascs are ther: entering the decomposer, as it is called. which the best results are obtained is abi this temperature the eupric chloride vol at lower temperatures the reaction veloe two-thirds of the hydrochloric acid is co Cuance-Ciaus Proc In the LeBlane process for making sodi sulphide is a by-product. & process for using this tank waste. Hi ealcium sulphide with earbon dioxide resulting hydrogen sulphide to sulphur ace: CaS + H.0 + CO2 = Cad QS +O, = 2S +2 Gossage failed because he could not getas CO, to staré with or a sufficiently concent: for the second stage of the process. This Chance in 1887, 1 Horrer: Jour. Sos., Chem. Ind. 2, 106 (188: * Jouuine: Catalysis and its Industrial Appli © 2010 As far back as R BY SOLID 53 treated cuprie chloride gen. In 1888 Deacon ful technical basis by d oxygen over pumice ts asa catalytic agent. of adsorption catalysis chlorine and cuprous RipvaL and Tayor: Catalysis-in“Pheory-and: Practice, 241 (1919). © 2010 Forgotten Books www. forgottenbooks. orgfe 56 APPLIED COLLOID CHE| uranium. ? apparently the best for laboratory w adapted for technical use.2 Judging by pure iron? is the catalyst generally e Using this material and with the aid of ments, it is said to be found possible to sure to the neighborhood of 50 atmos; is essential in the interests of efficienc prepared at a temperature not greatll the remaining substances which catalyz interesting are molybdenum and moly! alloys, and cerium with its congeners. hand, though related to osmium, possess activity. It was found that the activit increased by the addition of certain “promoters,” as they have been called, the oxides, hydroxides, and salts of the metals, us well as many other substan nature. In many cases just a trace of enhances considerably the activity of the| the catalysts appear to possess the cay There are no data toshow whether these so} the degree of adsorption of any of the the reaction or whether they prevent a catalytic agent. Mannich and Thiel® sta the adsorbing power of palladium for MISTRY While metallic osmium and uranium carbide are rk, they are not well the most recent patients, ployed in this proccss. various minor improve- Jower the working pres- heres. In all cases, it , that the catalyst be exceeding 600°. Of the reaction, the most. dates, tungsten and its (Platinum, on the other es but a slight catalytic of the catalysts ean be foreign bodies. These include various metals, Wkali and alkaline earth ces of the most varicd he contaminating body catalyst. Moreover, all acity for invigoration.* called promoters change ubstances concerned in assible sintering of the le that charcoal increases hydrogen. Rideal and Taylor® consider that the promoters may cause the relative adsorption of the reacting substances to ratios more closely. The contact ammonia process is very| Among the harmful substances are sulpl phosphorus, arsenic, boron, and their ¢ compounds; lead, zinc, bismuth, tin, etc, 1 Hanpn: Jour. Soc. Chem. Ind., 33, 54 (191 2 Jouning: Catalysis and its Industrial Appli 2 Cf Jeuuinex: Zeit. anorg. Chem., 71, 121 ‘Prasn and Tavzon: Jour. Phys. Chem. 24, $ Jour. Sor. Chem, Ind., 85, 548 (1936). * Catalysis in Theory and Practice, 29 (1919) 7 Jonzina: Catalysis and ite Industrial A ppli proach the theoretical susceptible to poisons. ur, selenium, tellurium, pounds; many carbon * Such minute quanti- De ations, 42 (1916). i911). 241 (1920). bations,.44 (1916). © 2010 Forgotten Books www. forgottenbooks. orgADSORPT 10: OF GAS OR VAPOR BY SOLID 57 ties of any of the above-mentioned substances as are to be found almost always in the [purest commercial products and so-called pure gases are suflicientt to diminish the catalytic efficiency very seriously. For instan in iron renders it ne: enormous value to the| Osrw. In 1830 Kugelmam to nitric acid in prese: the process was put on nominal reaction may but the real reaction then oxidized to. nitr into nitzic acid, 4NH3 + 702 =4NO + e, an impurity of 0.01 pereent sulphur rly uscless. The Haber process was of Germans during the war. Lp Nirric Acip Process p' observed that ammonia can be oxidized ice of platinum. About eighty years later semi-commercial basis by Ostwald. The ibe written NHs + 202 = HNO; + H,0; is the formation of nitric oxide, which is gen peroxide, and afterwards converted 6H.O + 20: = 4NO2 + 6H,O = 2HNO;+ 2HNO, + 411.0 The problem is complicated by the apparently simultancous oxidation to nitrogen, 4NH It is more likely that ammonia, by nitric oxid 4NH. Both the reactions are the reaction yielding n than the reaction givil obtained by keeping agent for as short a the reaction producing nitrogen being a secondary one. the two reactions took sets of products shoul the gaseous mixture. volumes of air is pasg 1 Jomuxe: Catalysis ay la reaetion which is usually written ls + 30, = 2N2 + GH,O the disturbing reaction is an oxidation of e,? perhaps + 6NO = SN; + 6H,0. accelerated by platinum; but, fortunately, itrie oxide takes place inuch more rapidly g rise to nitrogen. The best results are the gases in contact with the catalytic lime as possible, which is an argument for if place simultancously, the ratio of the two be indopendent of the rate of passage of A mixture of ammonia with ten or more ed ut a velocity of 1-5 meters por second id its Industrial Applications, 45 (1916), 2SapaTinr and SenpERENS: Comptes rendus, 136, 278 (1902). © 2010 Forgotten Books www. forgottenbooks. org58 APPLIED COLLOID CHEMISTRY through a plug of platinum gauze, 1-2 cm in length/and kept at 300°. This gives a period of contact not exceeding 0.01 sec. Under favorable conditions an 85 percent conversion off ammonia is claimed. Better results have been obtained in this| country,) with scveral layers of platinum gauze,? the yield rmmning 92 percent, with a fiow of 250 cubic feet per minute. The average concentration of ammonia is 10.7 percent. A smooth] platinum gauze is not effective. After some time it becomes roughened and activated. Contrary to what Ostwald had believed, a high temperature, say above 825°, is better than clover one. Phosphine is a bad poison, having a distinet cffcet ¢ven when present three parts per hundred million, but cyanogen cpmpounds are not bad because they oxidize readily. Iron oxide, grease, oil or tar must be kept away from the platinum gauze and a new gauze should be washed with pure gasolene or ether bdfore being activated. Ammonia from any source can be used though Landis* claims that the platinum must be activated anew when changing to a different ammonia. Sanarine’s HyproGENATION PROCESS Sabatier and Senderens* discovercd, a number of years ago, that reduced nickel will cause hydrogen to combine with ethyl- enc or acetylene forming ethane. This has since developed into a general hydrogenation process.> The principle of the method is a simple one. The vapor of the substance to be|reduced is mixed with hydrogen and passed directly over specific metallic catalysts maintained at temperatures usually held between 150° and 300°. The process is extremely rapid, since complete hydro- genation occurs during the short time the mixture is passing over the catalyst. Rapidity, however, is not the only advantage, for Sabatier and his collaborators, Senderens, Mailhc, ahd others, who have worked on this method for some fifteen yedrs, find it to be one which, whilst requiring the minimum of |attention, furnishes very high yields. 1 Pansons: Jour. Ind. Eng. Chem. 11, $41 (1919). 2 Parizy: Jour. Ind, Eng. Chem. 12, 5, 119 (1920), * Trans. Am. Electrochem. Soe., 35, 300 (1919). « Comptes rendus, 124, 1358 (1897); 128, 1173 (1899). § Josiiva: Catalysis and its Industrial Applications, 68 (1916); SapatmeR: Die Katalyse in der organischen Chemie, 44 (L914). © 2010 Forgotten Books www.forgottenbooks. orgADSORPTI: The metals which platinum, iron and ¢ most active, while th As would be anticipai largely upon the cont be prepared by reduct the nature of the oxi it is reduced. In g greater the activity, arranged to satisfy this requirement. perature is found to sensitive to external i ture reduces the catal a suitable intermedi, finds that the best nj ving the metal in ni heat, and then redu| about 300°-325°, un nickel has been prep} out of contact with quickly loses its acti Weight for weight, as that which has ha} soine suitable carrier. combining the cataly} ranging from pumice} The materials used| pound, naust be as pr readily adsorbed by| tivity. Sulphur and gens,! are particularl lesser degree, arsenid pounds. purity, appears to b sooncr or later, suecu} impossible to remov quent renewals necds ‘ The nickel oxide mus great difficulty of washin| Electrolyti¢ iV OF GAS OR VAPOR BY SOLID 59 are suitable as catalysts are nickel, cobalt, pper, of which nickel is far and away the others are arranged in diminishing activity. ied, the practicability of the methed depends ition in which the metal is used. It must ion of the oxide, the activity depending upon de employed and the temperature at which meral the greater the surface exposed the so that the conditions must be carefully Reduction at a low tem- yield a metal which is too active and too fiuences, while reduction at a high tempera- lytic action almost to zero. Consequently, te temperature must be chosen. Sabatier Icke for the purpose is produced by dissol- ric acid, calcining the nitrate at a dull red sing the oxide slowly at a temperature of ki Water is no longer evalved. After the red as described, it is necessary to keep it tthe air, as it is extremely pyrophorie and ‘ity on exposure. the efficiency of pure nickel is not so great \q its active surface increased by the aid of Henee many proposals have been made for st with a great variety of supporting bodies, and kieselguhr to charcoal and sawdust. , whether hydrogen, metal, or organic com- ure as ean be oblained, for any impurity is the catalyst to the detriment of its ac- lits volatile compounds, as well as the halo- to be aveided in this respect, and, to a and phosphorus with their volatile com- hydrogen, or hydrogen of equivalent essential, Even then the catalyst must, b to the toxic cfiects of minute impurities 3 in consequence, the desirability of fre- emphasis. {t not. be prepared fromn the chloride because of the ff out the.last traces, of adsorbed ehloride. © 2010 Forgotten Books www. forgottenbooks. org60 APPLIED COL. Of practical importance is fieial perfumes by the aid of LOID CIEMISTRY fhe preparation of numerous arti- his reaction. Moreover, it permits of the production of cyelohexanol and p-methy] cyclohexanol, easily obtained from phenol ai used in the manufacture of i therefore, destined to play am of rubber. d p-cresol respectively, which are oprene and butadiene, and seem, important part in the synthesis Probably the most important technical application of Saba- tier’s hydrogenation process i unsaturated fatty acids such ag acids such as stearic acid. process does not belong st: head of gas reactions acceler inerely refer to it because it is| principle. Sanatier’s Deny Attention has already been may split off hydrogen or wa’ ing on the nature of the catal: such as copper, cobalt, nick catalyze almost exclusively also do some anhydrous oxide oxides of manganese, tin, urani cadmium, though the activi iT at a given temperature, depend- to the conversion of liquid and oleic acid? into solid and saturated the acid is not vaporized, this ictly speaking under the general uted by solid catalytic agents, so I a further development of the same POGENATION PRocEss drawn to the fact that. aleohols icagent. Finely divided metals, 1, iron, platinum, and palladium lhc dehydrogenation process. So , chief among which are the lower ium, molybdenum, vanadium, and of these is less than that of the metals. The dehydrogenation of alcohols, both primary and secondary, is most readily e fatty aleohol be passed over t! at least 50 percent aldehyde or| tected by reduced copper. If a his catalyst at 200°-300°, a yield of ketone can usually be condensed. Cyclic alcohuls may be dehydrogenated in a similar way. Borneol, for instance, can be sage over reduced copper at conditions gives citral. The in the treatment of certain cam 1Ci, Exurs: Jour, Soc, Chom, I 771 (1914); Buus: Jour. Ind. Eng. gonation of ils, 2nd Ed., 108 (191 + Jonuaxe: Catalysis and its Ind transformed into camphor by pas- 50°, whilst geraniol under similar ormer fact is utilized industrially phors which are sold very cheaply Ind., 31, 1155 (1912); Suaw: Ibid., 33, Chem., 8, $86 (1916); Bunis: The Hydro- strial Applications. 82 (1916). © 2010 Forgotten Books www. forgottenbooks. orgADSORPTION OF GAS OR VAPOR BY SOLID 61 on account of their large content, of borneol. As the usual] proc- ess for removing borneol by means of nitric acid is very slow and unsatisfactory, the above dehydrogenation method, which yields nearly pure camphor, has found ready application ip this field. Of the other eatalysts, cobalt, iron, platinum, as well as the above-mentioned oxides, are less advantageous. Zinc is stated to possess high activity. Nickel is ruled out on aceount of the violence of its reaction, for it pushes decomposition too far. The most important of the industrial applications of this reaction is the preparation of formaldchyde from methyl] alco- hol. The earliest recorded production of formaldehyde] is to be found in the elassic experiment of Hofmann’s (1867), in which a red-hot coil of platinum wire suspended over methyl alcohol in a beaker continued to glow there so long as it is in eontaet with a mixture of the vapor and air. This method forins the basis of most of the subsequent attempts and of the present eommercizl process, Air is driven through wood spirit kept at a temperature suitable for saturation and the mixture then passed info the eatalyzer, usually copper gauze. In the so-called oxidation of methy! alcohol, the primary reaction is the splitting-off of hydrogen? and the practically si- multancous depolarization by oxygen, 2CH.0H + 0. = 2HCHO + 4H + 02 = 211CHO + 2H.0. Hofmann? found that osmium tetroxide oxidizes alcohol to aldehyde but not to acetic acid, acting apparently as a carrier for oxygen. If is probable that we have here a catalytic splitting of the alcohol, the nascent hydrogen reacting with the osmium tetroxide. Wieland* considers that the contact sulphuri¢ acid proecss really involves a dehydrogenation, the reactions be 80, + H.0 = H:80; FSO: — 803 + He 2H, +- Op = 2H,0 ing: 1TwonrE: Dietionary of Applied Chemistry, 2, $92 (1912). 2 LpBuane and Prascuxe: Zcit, Elcktrochemie, 17, 47 (1911). 2 Ber. deutsch. chem. Ges. 48, 1057, 2854 (1913). * Ibid. 45, 685 (1912). © 2010 Forgotten Books www.forgottenbooks. org62 APPLIED COLLOID CHEMISTRY Surrace Comsustion The subject of surface combustion has been developed by Bone in England! and by Lucke in America. Bone began by a study of the combination of hydrogen and oxygen in contact with hot surfaces of| porcelain, magnesia, silver, gold, platinum, nickel, calcined spathic iron ore (containing 79.0 percent ferric oxide and 14.5 percent manganous oxide), nickelous oxide, and copper oxide. With each of these surfaces the rate is proportional to the pressure of the dry gas when electrolytic gas is used, is ap- proximately proportional to the partial pressure of hydrogen when either gas js present in excess, and is increased by a previous treatment with hydrogen, In the case of porcelain, Bone dlecides that porous porcelain oecludes or condenses both hydrogen and oxygen at tates which depend to some extent upon the physical condition or past history of the surface. While the process is extremely rapid in the case of oxygen and the surface layer is soon saturated, the occlusion of hydrogen is slower and the limit of saturation much higher. Combination between the occluded gases occurs ata rate cither comparable with, or somewhat faster than, the rate at which the film of occluded oxygen is renewed, but considerably faster than the rate of occlusion of hydrogen. In later papers Bone? showed that all incandescent substances are capable|of aceclerating gaseous combustion; and to an approx- imately equal degree, for the wide differences between the catalytic powers of various surfaces at low temperatures gradu- ally diminish as the temperature rises, until at incandescence they practically disappear. If an explosive mixture of a combus- tible gas and air is pressed through the pores of a granular, high- nelting solid, and if the issuing gas be lighted, it will speedily raise the granular solid to incandescence if the conditions are right, after which the heated surface will accelerate the rate of combustion so much that the whole of the gas will be burned at the surface of the solid and we shall have what has been called flameless combustion. As a matter of fact there is flame, but the flame is so short and the light from the incandeseent solid so intense |that there seems to be no flame. The combustion 1 Phil. Trahs., 206A, 1 (1906); Jour. Franklin Inst., 173, 101 (1912), 2 Summarited in Ber. deutsch. chem, Ges., 46,5 (1913); JopiiNa: Catalysis and its Industrial Applications, 51, (1916)... © 2010 Forgotten Books www.forgottenbooks. orgADSORPTION OF GAS Ok VAPOR BY SOLID takes place only at the surface lays over the surface and not as flame; The advantages of this surface co localized heat, combustion with im development of a large amount o! By passing the explosive mixture we get an incandescent surface wl 63 r of the granular solid but all between each solid particle. bustion are an intense and 2 nimurn excess of air, and the the heat as radiant energy. through a porous diaphragm ‘ich can, if need be, be held glowing side down over a solution which is to be evaporated. In this way, it is possible, for ing glass solution without danger of b forms as a solid film on the surfa removed fram time to time. ‘Thi very suceessful in making candy. The granular mass may be piled! boiler tubes giving an extremely hi temperature depends on the work refractory material is determined Under ordinary conditions calein used; but when high temperature all solids are eliminated except cal dum. liquid fuel for a gaseous fuel. It i ful applications of surface comb where the heat is radiated very qu of the refractory does not rise wa packed in refractory material for ix furnaces have proved very useful i tance, to evaporate a water- umping. The sodium silicate e of the solution and can be form of heating has proved in round a crucible or around igh efficiency. The maximum ng conditions. The choice of y the temperatures involved. d fire-clay, ganister, ctc., are & are in question, practically ined magnesia and carborun- Attempts are now being made to substitute an atomized stated that the most success- istion to large scale work are ickly so that the temperature uly—with steam boiler tubes stance. Surface combustion annealing shell. Since an explosive gas mixture is used, it is necessary to keep the flame from working back an: refractory instead of on the surfa ing the rate of flow of the gaseous n} several ways of doing this by spec! Werspacn Gas The invention of the gas mant. continue to compete with elect: 1 Spacer: Jour, Franklin Inst., 177, 3 + Reports of Progress of Applied Chen} ? Jour. Ind, Eng, Chem, 5; 801 (1913)! burning in the mass of the Bone does this by regulat- ixture. Lucke* has described al construction of the heater. Mantnn lc made it possible for gas to city as an illuminant. The 7 (1914), istry, 1917, 26. © 2010 Forgotten Books www. forgottenbooks. org64 APPLIED \OLLOID CHEMISTRY best results are obtained when the Welsbach gas mantle consists of 99 percent thoria and a relatively poor light, b| gradually increases the ly when 1 percent is present| ishes the luminosity unti. effect is inappreciable. In| silk or ramie web is impre, solution of thorium and 99:1, together with a littl nitrate, if necessary. We are dealing with surf. lime light and of the Wels decay of the light of the | similar though much slowe manile. when new; but the light de While a thoria mantle rea power is low. Ceria has spectrum; but the energy o! ature of @ ceria mantle doe. L percent ceria? Pure thoria gives % the continuous addition of ceria iminosity to a maximum of ten-fold Any further addition then dimin- |, with 10 percent the difference in present-day manufacture, the cotton, nated with a 25-33 percent aqueous rium nitrates in the proportion of e hardening medium, eg,, beryllium ee combustion both in the case of the buch mantle, as is shown by the rapid me light owing to sintering? and the w decay of the light of the Welsbach Mantles of magiesia and lanthana give a good light creases as the surface becomes glassy. hes a high temperature,? its emissive high emissive power in the visible radiation is so great that the temper- not rise high enough. Starting with thoria and increasing the amount of ceria increases the emissive power but lowers the tempd luminous efficiency is obtal due to the ceria is balanced inantle due to the increas solid solution with the th show whether equilibrium ature of the mantle. The maximum ined when the rise of visible emission by the drop in the temperature of the d vadiation. The ceria may form a ria but there seem to be no data to is actually reached in the mantle. 1 Jonuina: Catalysis and its Industrial Applications, 62 (1916). 2 Sreismerz: Radiation, Ligh ‘Ives, Kinassury and Kai (1918). tand Illumination, 92 (1909). mer: Jour, Franklin Inst, 186, 401, 585 © 2010 Forgotten Books www. forgottenbooks. orgCHAPTER IT ADSORPTION OF VAPOR BY LIQUID AND OF LIQUID AND SOLID BY SOLID AND LIQUID ADSORPTION OF Varor BY Liquip Campbell! believes that one source of error in the method determining molecular weights by the so-called air-bubblin| method is due to the formation of a film of adsorbed air on ti] surface of the solution which imierferes with the evaporatio! Ie deduced the existenee of an adsorbed gas film from his quaitl- tative measurements on evaporation. The existence of such film is shown directly by Rayleigh’s experiments on liquid jets|? A vertical jet of water or any liquid slows up and breaks into drops when the head is sufficiently great relatively to the dia meter of the jet. These drops scatter because they rebount when they strike one another. If a fecbly electrified body brought close to the jet, the jet becomes coherent. Under mo: powerful clectrical action the seattering of the drops becom even greater than when there is noclcctrification. Whathappen is that there is formed round each drop a film of adsorbed ai which prevents two drops from coalescing when they collide. When the drops are electrified, the air film is removed to such exteut that the drops come more nearly in contact and coalesce. With higher electrification, a marked charging of the drops tak place and the repulsion of the like charges causes the drops 4 scatter, Nipher® states that drops of 1 mm radius do not attra¢ each other when charged to 0.0031 volt. That there is an al film between the drops can also be shown by letting two jets in} pinge ander such conditions that they bound apart. It w: found that whenover the jets rebounded, the electrical insulati was practically perfect. Rayleigh found that presence of dust Poe an E38 TES SE S 1 Trans. Faraday Soc., 10, 197 (1915). + RayuEran: Proc, Roy, Soc., 28, 406; 28, 71 (1879); 34, 130 (1882). # Seience, 34, 442 (1911). 5 G5 © 2010 Forgotten Books www.forgottenbooks. org66 APPLIED COLLOID CHEMISTRY or addition of a drop of milk had a marked effec with which the drops coalesce. The reason for this worked out. In Worthington’s experiments on splashes! the film plays an important part. A drop of water sheet of water in such a way that the drop passes b} face, becoming completely submerged, and then head of a column of adherent liquid with the a apparently unwetted by the liquid with which it has When the water drops from an oar on the recover, what are known as rolling drops? which depend o1 of adsorbed air films and which are also sensitive t of electrified substanecs. Tf the surface of a sheet of water is covered wi ascutn of oily soot or of plankton organisms, a mis| deposit drops on the surface which will be cxtreni This phenomenon is not at all uncommon at La on the ease lnas not been ladsorbed air ay fall on a low the sur- crges at the pper portion een covered, we often get the presence the presence fh oil or with or fog may ly persistent. ke Mendota at Madison and bas trequenily been observed elsewhere.? Sinee soap-bubbles are hollow drops, they sho’ Id behave in soine respects Like liquid drops, though not necessatily like drops of a pure liquid. It is possible to press two soap bul with considerable foree without causing them bles together Ito coalesce;* but if they are electrified slightly, they coalesce readily without bursting, Tt is interesting to note that water will apparentiy remove a film of adsorbed air mueh more readily from a poh of ivory or marble than it will from a water surfac ished surface 3° but we do not know whether this is true for all solids. Sakulka® obtained somewhat different results with lead shot, but t been because they were not polished. Tf a vapor is adsorbed by a liquid, it will conden| filn at a temperature above that of the normal dew } Wortuiarow: Proc. Roy. Soe., 34, 217 (1882). 2 Osnorxu Revnows: Chem. News, 44, 211 (1881); Kars 68, 681 (1894). a Jupay: U. 8, Monthly Weather Review, 44, 65 (101 Jour. Meteorological Sov., Japan, 36 (1917). «Boys: Phil Mag. 26, 409 (1888). + Worruineron: Prog, Roy. Soc., 34, 217 (1882). * Drude’s Ann., 25, 892 (1908). © 2010 Forgotten Books is may have ke to a liquid point. Can- br: Wied. Ann., ); Nakamura: www. forgottenbooks. orgADSORPT: tor! realized this with v oil which is not a well-d ADSORPT! If a liquid is adsorbed and we say that it wet: by a solid, it does not deal of question wheth angle, the contact angl Lord Raylcigh® states di angle is zero, and this liquid is adsorbed by t. over the surface of a accepted fact that the r pendent of the nature oi seemed a very improbal be justified by the fact ¢ quite simple when we come in contact with thy are really dealing with makes no difference wh of the liquid tube. Thay from the fact that cone liquid is allowed to rise ION OF LIQUID BY SOLID 67 ater and mercury and Clark? with olive fined and reproducible liquid. oN oF Liquip By SoLip at a solid surface, it forms a liquid film the solid. If a liquid is not adsorbed vet the latter. There has been a good the liquid meets the wall at a definite , or whether the contact angle is zcro. lefinitely that in his opinion the contact must be true if we consider that the le solid. The formation of a liquid film etted solid accounts for the generally isc of a liquid in a capillary tube is inde- the walls of the tube. This has always at it wasso. The whole thing becomes consider that the rising liquid does not eb walls of the capillary tube atall.3 We lhe rise of a liquid in a liquid tube and it material is used to support the walls this is the real explanation may be seen rdant results are not obtained when a ina dry tube. To get good results it is th state of things and one that could only important to immerse the tube in the liquid and then to raise it. Bigelow and Hunter’ el: im that the nature of the walls does have an effect on the capillary rise; but their experiments were not done in a eapillary tube| On the assumption th: liquid must rise to the t and diameter of the tu by Lord Rayleigh.” ¥ 3 Wied. Ann., 56, 492 (18! * Proc. Am, Acad., 41, 36 3 Scientific Papers, 3, 393 * Of. Hankins and Brow} 5 Raynzicu: Scientific Pal ® Jour. Phys. Chem., 15, 7 Scientific Papers, 3, 52! | t the contact angle is cro, a thin film of p of the tube, irrespective of the height e. This has been recognized explicitly Ihen the liquid does not wet the solid, 5). (1906). (1902). + Jour. Am. Chem. Soc., 41, 522 (1919). lpers, 8, 421 (1902). 67 (1914). 3 |(1902). © 2010 Forgotten Books www. forgottenbooks. org68 APPLIED COLLOID ( inercury and glass for instance, the as} angle leads to at least one awkward ¢| of the meniscus is certainly not in ¢| therefore none of the mercury is in cor have a glass tube, infinitely long, close with mercury, we must conclude, if logical, that the colunin of mercury any point and that it stands alone, film of air, mercury vapor, or sole Personally, I feel no desire to be so loki me probable that at some point the fo all the vapor layer and that the mer with the glass. This is the more ecr the mcreury sometimes tends to hang i} and this could not happen if the me: with the glass. BMISTRY umption of a zero contact melusion. The upper part patact with the glass and tact with the glass. If we id at the bottom, and filled ‘© are going to be strictly os not touch the glass at Jor fn on all sides by a thing whieh is not glass. ical as that. It seems to ree of gravity squeezes out ury does come in contact in because we know that afreshly-made barometer hcury were not in contact For a liquid to wet a solid in the presence of air, the liquid must be adsorbed more strongly than the Hofmann! gives a number of details as some liquids displace adsorbed air fro eases heating is necessary to get q powder is distinctly difficult to wet. strongly and is not wetted readily by alcohol, the alcohol displaces the air a) more easily by water. The floating pieces of metal on water is due to the wets them. The Cape Cod lighter ¢ol in a brass handle. When this is dippt air and must displace it. ito the slowness with which 1 certain solids. In some ick results. Lyeopodium Gum arabic adsorbs air water, If ground with d then the guin is wetted lof metallic powders or of slowness with which water sists of a porous stone set ed into a ean of kerosene, the kerosene is sucked rapidly into the pores displacing the air. The light is taken out, lighted, and wood fire. The adsorbed kerosene bu enabling one to do away with paper Another interesting application of the solid is the ease of solidified bromine earth saturated with bromine, which laced uncer the logs of a ins for about ten minutes, and even kindling wood. ladsorption of a liquidbya 2 Tt consists of siliceous lan be driven out by heat. Of nore technical importance is the adsorption of fused magne- 1 Zeit, phys. Chem., 83, 385 (1913). cit. anal. Chem., + Outlines of Industrial Chemistr 26, 222; Jou} . Chem. Soc., 62, 688 (1887). 25K (1916). © 2010 Forgotten Books www. forgottenbooks. orgADSORPTION OF LIQUID BY tite by chromite. ‘Ihe simple form of magn a lower, negative, magnetite terminal and an w OLTD 69 tite arc consists of per Hon-consuming terminal of copper, of such size that it does not get so hot as to oxidize or evaporate, but. sufficiently hot to of magnetite vapor. When the are is struc. iaguetite forms on the surface of the magnet are-conductor issues from a depression in this straight magnelite are flickers badly; but thi void condensation ; @ pool of melted ite terminal and fhe melted pool. The Is can be overcome by mixing the magnetite with some more refractory material, such as chromite. The chromite remains melted magnetite as a sponge does water. In have been made steady and thereby suitabl¢ We are quite familiar with the fact that gla jolid and holds the this way, these ares for industrial use. s must be cleaned before it can be wetted satisfactorily by water; but it is not so well known that platinum is only wetted by m weury under special conditions.? ‘Mercury, which holds even al very little sodium in solution, has the power of wetiing platii markable manner. The appearance of the similar to that. presented by amalgamable met mercury. But the platinum is in no wise g the amalgam may be washed off by clean mort um in a very re- platinum is quite als in contact. with ttacked, J*urther, ury, and the latter will also continue to adhere closely to the platinum. All the phenomena of capillarity are presented betw surface of the mercury in a platinum eup concave; and a basin of mercury may be em; of similarly prepared platinum foil be laid icon the two. The prepared is quite ptied if a few strips ver its edge—just as a basin of watcr may be cmptied by strips of paper or cloth, and under the same condition, namely that ¢| such capillary siphon be longer than the sodium removes the oxide filn and permits t in contact with the platinum.” It is found that iron, copper, bismuth, and| wetted by mereury if their surfaces are first t ainalgan. A few years later a technical application was made. Kirchman? reports thet sodiuut 2Srainmers: Radiation, Light, and lumination, *Gurunin: Proc. Roy. Soc., 13, 458 (1864). + Jour, Chem, Soe., 26, £18 (1873), he external limb of internal one. The l¢ Mercury to come antimony are also uched with sodium f this observation amalgam can be 10 (1909). © 2010 Forgotten Books www.forgottenbooks. org70 APPLIED COLLOL IP CHEMISTRY used advantageously in simplifying the method of dry-gilding iron. Surfaces of iron and simila) are immediately amalgamated by| Gold chloride in concentrated s on the amalgamated surface, and heat of lamp or fire. A very un} permitting a high polish. Corr with silver and platinum salts, Wald! has pointcd out that th vapor pressure of a liquid, when quently, if water really wets ice, tube made of ice, the vapor pressu} of wetted ice at the same temper; into aecount in books on the phi eapillarity, gravity, etc., are usu: The adsorption of a quid filr in the determination of the speci are weighed in a highly divided st pointed out that platinum in the si between 21 and 22 while a valuea r metals, even though oxidized, simply rubbing with amalgam. lution is then applicd quickly the mercury volatilized by the iform gilding is thus obtained, sponding results are obtained ere must be a lowering of the a liquid wets a solid. Conse- or if water rises in a capillary re of dry ice will differ from that ture. This point is not taken se rule because effects due to lly ruled out explicitly. may introduce quite an error fic gravity of bodies when they te. As long ago as 1848 Rose? tate of foil has a specific gravity ove 26 was found for platinum precipitated from the chleride by sodium carbonate and sugar. Similar though less extreme diff silver, and barium sulphate. T assume thai the powder is not conjunction with a film of conde: It was Edward Lear who wrot to sea in a sieve. He considere: modern science is almost equal t water in a sieve. If we take a the meshes, air can still pass read: does not wet the wires and con: vents it from passing through freed from water by filtering th: We can carry water in such a si 4 Zeit. phys. Chem., 7, 514 (1891). 2 Pog, Anm., 73, 1 (1848); Jour, Chi 38ec however Jounston and ADA (1512) 4 Cawousox: Lehrbuch der Physik, 5 Campsie: Jour. Ind: Eng. Chem, © 2010 Forgotten Books erences were found with gold, is can be accounted for if we weighed alone in water but in sed water. : about the Jumblies who went cd that a nonsense rhyme; but. the problem, for we can carry ine-meshed metal sieve anc oil ily through the holes; but water equently surface tension pre- he holes. Gasolene may be ‘ough a 200 mesh metal sieve. , eve? if we do not fill it too full; m. Sov., 1, 182 (1849). 3: Jour, Am. Chom, Soe., 34, 568 A ILL, 613 (1907). 6, 762 (1919). www. forgottenbooks. orgADSORPTION OF LIQUID BY SOLID 71 but an Joiled sieve is not a perfect substitute for a pail. This principle has received an important technical application in the shower-proofing of textile fabrics. The fibers are coated with some wpter-rcpellent hydrocarbon, wax, or salt, in which case the fabric will be porous to air but will shed water up to a eertain point. All campers are familiar with the unpleasant fact that atent will leak in b rain if one touches the canvas with one’s finger. The tent is |shower-proof and not water-proof. When one pushes against |the tent, it either contracts or expands the air spaces. If the air spaces contract, air is driven out and when the finger is taken away, water enters. If the air spaces expand, water runs in.) Either way the air is displaced at that point and water enters, | What happens can best be seen from an analogy. If one dips a fountain pen filler into ink and presses the bulb, air is driveh out and ink enters when the pressure is relieved. If one pinthes the bull before dipping the glass end into the ink, no air bubbles out but ink gocs in as soon as the pressure is taken off. It|}makes no difference therefore whether one touches a tent frdm the inside or the outside. In either case, water is drawn ihto the pores of the fabric and the tent leaks continuously onee thé air is displaced. Awnings on a boat usually leak where they regt on a wooden or iron support. This is because there is always ¢nough wind or vibration to be equivalent to the touching of the thnt with the finger. For the same reason, a tent is apt to leak argund the pole. The reverse case is to be seen in the ordinary watcr wings. They ale made of a fine-meshed fabrie which is first thoroughly wetted so that a film of water is formed in the pores. The strengt} of this water film is so great relatively that one can blow up the water wings without the air escaping and the water wings will support 2 grown person without difficulty. Ehrenberg and Schultze® point out that many powders, when onee thproughly dried, are not easy to wet. After a period of drought, drops of rain will often roll along the dust without wet- ting it.| Even in the ease of a shower the dust may be only weticd |to a depth of less than a quarter of an inch. ‘This is *C. O] Wener: Jour. Soc. Dyers and Colourists, 17, 146 (1901). 2 Zeit, [Kolloidchemic, 15, 183:(1914). © 2010 Forgotten Books www.forgottenbooks. org72 APPLIED COLLOID CHEMISTR shown by Ehrenberg and Schultze to be due|to the adsorbed air on the surface of the solid. Any treatment| which cuts down the amount of adsorbed air makes the dust, pr soot, or other substance, more easily wetted. It is not easy to wet carbon black with wat ; but if the oily material is driven out by a preliminary treatrpent with super- heated steain, carbon black is dispersed by wt and the liquid bubbles tike soda water owing tot! adsorbed air. If a 50 ce vessel is filled wit er very rapidly he escape of the good cocoanut charcoal and if water is then added until the vesspl is full up,to the mark, 150-200 ee of air will be driven off. A case analogous to that of the oiled sieve ht Iding water has been described by Lord Rayleigh! who found thet a piece of iron gauzc pressed down upon the flat bottom of a glas s vesscl, holding a shallow layer of mercury, remained on the bottom of the vessel and did not risc through the mercury. It is quife clear from this that one could carry mereury in an iron sieve. With sodium in the mercury the amalgam would rua through the gauze. Ray- Jeigh’s experiment of course would not succe| sodium amalgam instead of with mercury. d if tried with Since the adsorption of liquids by solids is selective, it follows that one liquid willbe adsorhed more by a solid than will a second liquid and that consequently the first |will displace the second from contact with the solid. No system) tic study of this phenomenon scems to have been made; but we|know that kero- sene will displace water in contact with copper and that water will displace kerosene in contact with quartz,? while alcohol will displace oi] in contact with metal? and linseed |oil* will displace water in contaet with white lead. According t this, one should use 4 rag dipped in alcohol with which to wipe off a lamp and it is for this reason that we cover metal surfaces wit] vuseline or with 2 heavy oil to prevent rusting. Parkerized or }hhosphatized iron is said to owe its non-rusting properties to an |oil filin. In the kitchen, people wet the moulds before putting |n corn starch or gelatine, and they butter the pans before making 1 Scientific Papers, 4, 430 (1903). 2 Homann: Zeit. phys. Chem., 83, 385 (£912). 8 Poceens: Wied. Ann., 67, 669 (1899). fudge, or grease 4‘ Crorcxsiank Sart: The Manufacture of Paint. 92 1915). © 2010 Forgotten Books www. forgottenbooks. orgADSOR! the griddles before ni num griddles do not oxide film keeps the ought to apply to fr and apparently does to oil the dies wh earth is excellent? foi poses. Even very when rubbed with in! of the methods of re selective adsorption. There are almost Graham* made a fe sorption of liquids b, in a liquid for an he few seconds betwee! parts of palladium f of alcohol, 1.7 of eth benzene, 10.2 of cas Quite recently Mat. essential oils from a Sinee the adsorpti sorbed more readily application of this is egs. silver iodide and it is mercury condenses light. I have seen ture condensed so 7 seemed as though a If the adsorption Gelatine is adsorbed drying will often te 2$incox and Suvrn: 2 Koran: The Utiliz @Lawe: Jour, Phys. PTION OF LIQUID BY SOLID 73 aking flapjacks. Jt is claimed that alumi- need to be greased because the air in the akes from sticking; but the same reasoning ying-pans when uscd for the same purpose not. In making pottery, it is the practice m making dust-pressed ware.! Infusorial : cleaning glass plates for photographic pur- greasy plates become clean very rapidly usoriul earth moistened with water. Some moving grease spots from clothes depend on o quantitative data on selective adsorption. y rough measurements on the selective ad- palladium. A piece of foil was immersed ur and afterwards dried by pressure for a folds of blotting paper. One thousand il were found to retain 1.18 of water, 5.5 or, 0.54 of acetone, 4.5 of gylcerine, 3.5 of tor oil, and 18.1 of oil of sweet almonds. hers’ has shown that lead adsorbs certain jueous solution. n is selective, a vapor or liquid will be ad- by one surface than by another. A striking to be found in the old daguerreotype proe- The latent image is formed on a plate of silver coated with leveloped by means of mercury vapor. The nm the places which havc becn exposed to patched cement cellar floor on which mois- arkedly on the weathered portion that it ipe had broken under the floor. is very marked we may get intense strains.® so strongly by glass that the gelatine film on x off the surface of the glass. On the other Trans. Am. Ceramic. Soc., 14, 658, 567 (1912). tion of Waste Products, 310 (1915). them, 20, 761 (1918). 4 Jour, Chem. Soe., 20, 278 (1867). * * Trans. Am, Electrochem. Sos., 34, 271 (1917) ©Granam: Jour. Chel Soe, 17, 320:(864). © 2010 Forgotten Books www. forgottenbooks. org74 APPLIED| hand, it docs not adhere agar we get a state of concentrations. Certain! glass while others appar the substitution of agar-} would be impossible on COLLOID CHEMISTRY ‘© plates of mica or caleite. With agar- lhings which appcars to vary with the agar-agar jellies will adhere reudily to mtly do not. People have claimed that gar for gelatine in photographic plates a technical scale, because the agar-agar film would slip off if the plates were set vertically to dry; but it is probable that this di the only drawback. ificulty would be overcome if that were The whole theory of adhesives depends in part on the fact that the cementing material 4, hardens there. It is they] he useful for a number of| metal, ivory, ete., while materials. Since the b for glass, cements for me} the differences in adsor ever made a careful stud. A good glue joint in we per square inch. We ard always realize that the t high if a decrease in the back as 1850 Berthelot! removed the air, sealed entirely full of liquid, an liquid continued to fill th it should be for the tem; 1/93 in the case of alcoll indicates a breaking str’ 100 atm. for alcohol and for aleohol. Stcfan* an: internal pressure of a hiqt strength and they obtai about 2000 atm. Som 1 Ann, Chim. Phys. (3) 80, 2 Phil, Trans., 183A, 355 ( ? Wied. Ann., 29, 655 (199 4 Sitzungber. Akad. Wiss. ¥ 5 Cf. Huuerr: Zeitphys, Chem...42 theres strongly to the two surfaces and lefore possible that one agglutinant may different materials, such as wood, glass, thers give good results only with special joks give different recipes for cements als, cements for metals and glass, ete., tion are real ones though no one has of agglutinants from this point of view. dod will casily stand a strain of 6000 tbs. quite familiar with this; but we do not nsile strength of liquid water is pretty ross-section can be prevented. As far filled 2 glass tube nearly full of liquid, jthe tube, heated the tube until it was allowed the whole thing to cool. The tube until the volume was larger than erature by 1/420 in the case of water, ol, and 1/50 in the case of ether. This in of about 50 atm. for water and over other. Worthington? obtained 17 atm. ‘Tumlirz‘ consider that the calculated id is a measure of the theoretical tensile In in this way a value for aleohol® of direct. measurements of the tensile 232 (1850). 392), ). ien., 109 Ia, 837 (1900); 110 1a, 487 (1901), . BBR TSNRY.. © 2010 Forgotten Books www. forgottenbooks. orgADSORPT strength of liquid films who found a maximum square inch for steel ent On the assumption that surface, this gives a tor square inch, or about si: Rice* reports that cel worked in the brick-1 remarkable way whenevy Rice does not explain w! of the clays was very hi The formation of glazi metals are cases in whi only adhere to the bj nearly enough the say the glass or enamel fr changes.* The adsorption of wat| liarities. Working in found that gelatine con immersed in liquid was saturated water vapor and other experiments pressure of water in gel ION OF LIQUID BY SOLID 75 have recently been made by Budgett,! weaking strength of about 87 pounds per kl-gauges held together by 8 water film. the water occupied only one-tenth of the sile strength of nearly 900 pounds per xty atmospheres. 'tain plastic clays from Montana, when laking machines adhered to iron in a er they came into contact with that metal. y these clays should stick to iron. One ‘h in silica, 76.8 percent. s on pottery and stil] more of enamels on h the fused or sintered mass must not se after cooling but must also have e cocflicient of expansion to prevent pm going to pieces as the temperature ier vapor by gelatine presents same pecu- IOstwald’s laboratory, von Schroeder* lined a thousand percent of water when er and less than 400 percent when in at the same temperature. From these. ‘on Schreeder concluded that the vapor latine must be higher than that of pure water, because water distills from the gelatine to the vapor phase. The reason for this ud gelatine has a cellular st; a space saturated wit! certain amount of wate for the water to conde water. will take up water as be and fill it. If the bag if the bag is so construe! the water will distill fr 2 Proc. Roy. Sov., 82A, 25 2 Trans. Am, Ceramic So ? Ranpav: Enamels and- * Zeit. phys. Chem., 48, 1 i expected phenomenon is possibly that ucture. Ifa dry paper bag be placed in water vapor, the paper will adsorb a ; but there will be little or no tendency se inside the bag and fill it with liquid If a similar bag is immersed in liquid water, the paper ore; but water wil] also pass into the bag is then lifted into the vapor phase, and ed that the actual dripping is negligible, m the curved surface in the bag to the i912). ., 14, 610 (£912). Enamelling, 101 (1912). 19 (1903). © 2010 Forgotten Books www. forgottenbooks. org76 APPLIED COLLOID CHEMISTRY plane surface in the containing vessel. The smaller the bag is, the greater will be the curvature of the water wit] quently the higher the vapor pressure. With th spaces in solidified gelatine, the vapor pressure of| water will be enough higher to counterbalance the Jevels in von Schroeder’s experiments. in and conse- microscopic the drops of difference of While this explanation accounts for the phenomena provided gelatine really has a cellular structure, a point wh ich is not yet generally accepted—it is superfluous if the facts are mot as stated. Wolff and Buchner! claim that the loss of water when gelatine is placed in the vapor phasc ts merely due to experimental error.” They have certainly shown the possibility of crror if von Schroe- der’s results; but they did no experiinents invol error as one must assume if von Schroeder’s data ing as much e worthless. The whole matter is therefore upin theairforthe present. Wash- burn’ found that moistened clay will dry prett: completely if suspended in a closed vessel above water. Tle aftributes this to the aetiou of gravity, This could only be true in ease there were no soluble salts in the clay and in case the pores were so coarse that the capillary rise was not equal to above the water level. There are other substances which seem to behave though no experiments like von Sehroeder’s have be Schwalbe states that cotton cellulose takes up, moisture in presence of saturated water vapor. Richards® find 17.7 percent adsorbed moisture wht phase is 97 percent saturated. By extrapolation t this might casily give about 21 percent moisture} and Richards incline to the view that the curve i the distance . like gelatine, in performed. 2L pereent Masson and m the vapor 100 perecnt but Masson asyluptotic, in which case the value would be infinite, which seoms absurd. Vignon® finds that one gram of cotton takes up abq of liquid water, while a fine-grained sponge willl nt five grains hold thirty grams of water per gram of sponge, and a coarse-grpined sponge ' Kon. Akad. Web. Amsterdam, 17, May 30 (1914); Zeit. pl 271 (1915), ? See also Arisz: Kolloidchemische Beihefte, 7, 87 (1915). 3 Jour, Am. Ceramic Soe., 1, 26 (1918). + Die Cheinie der Cellulose, 10 (1911). 5 Proc. Roy. Soe., 794, 421 (1906). © Comptes rondus, 127, 73 (1898). © 2010 Forgotten Books ys, Chem., 89, www. forgottenbooks. orgADSORPTION OF only about six grams. Leight will bold four grams of water wl Some of this water is held in cap) the surface of the cotton; a pa eotten; and some may be hi factory way of differentiating b Dry caseine takes up about I Infusorial? earth is able to take liquid. Wood flour will take u glycerine without running. may contain 90 percent of wats bibe as much as two hundred which is the reason that this m: for dressing wounds. If 2 freshly-broken piece o! against the tongue, water will be earthenware and the piece wil When water is drawn up into a and one at once wonders how LIQUID BY SOLID 77 n! states that absorbent cotton, hen centrifuged at 4000 R.P.M. ary spaces; some is adsorbed on tt is probably dissolved in the eld in cells. We have no satis- tween these possibilities. 25 g water per gram of caseine.? ip more than double its weight of over double its weight of nitro- librous peat, fresh from the bog, rand Sphagnum moss may im- imes its own weight of water,® ss is used largely in the trenches porous earthenware be pressed sucked up into the pores of the ll tend to stick to the tongue. capillary space, air is driven out much pressure the water will exert under these circumstances. Jamin® has made some pre- liminary experiments along, thi piece of dried chalk. Into thi: manometer and the hole was th| placed in water, the air was dis: sure of 3-4 atmospheres was ob| pressure because the amount of Jarge. A better methed woul line. A hole was bored in a hole was dipped one end of a len closed. When the chalk was laced from the pores and a pres- ained. This is not the limiting cad space in the manometer was be to determine the pressure neecssary for the air to force the water out of the pores of the chalk. Spring’ obtained pressures of| water displaced air in contact v Jamin, Askenasy, and Wied) 1 Jour. Phys. Chem., 20, 32 (1916). *Van Suyxe and Pusnow: Scien 179 (1913). ? Koter: Utilization of Waste Pr one-fifth of an atmosphere when ith sand. eburg® have deseribed different ee and Practice of Cheesc-Making, ducts, 310 (1915). +Kressman: Met. Chem. Eng., 14, 372 (1916), * Perey's Metallurgy: Puel,, 208 (1 ® Cuwoison: ‘Traité de Physique, ? Mem. Soe. helge Geologie, 97, 13 8 Wied. Ann., 59, 764 (1896) 75). Lil, 622 (1907). (1903). © 2010 Forgotten Books www. forgottenbooks. org73 APPLIED COLLOID CHEMISTRY forms of apparatus in which water evaporates t tube ora porous cup of plaster into dry air. Ast! rough a porous ie water evapor- ates off, mercury is drawn up into the tube reaching a height of 90 em without difficulty. If bubbles of air did not mercury could be drawn up to incredible height: tensile strength of the liquids. When considering the adsorption of water v: form, water or , limited by the por by cotton, reference was made to the heat developed. Attention might perhaps be called here to Meissner’s expcrime: developed when powders are wetted by liquids.! there was no appreciable difference in the heat water was taken above and below 4°. His quay were rather discouraging, however, because apparent relation between the amounts of heat amounts of powder taken, which must be the mental error. The more careful experiments o} that when silica, sand or glass is brought in con] at approximately constant temperature, the heat at 7° is approximately 0.00105 cal. per squ surface wetted. Foote and Saxton? find that water adsorbed supercools readily to —6° and is not all frozen al once frozen, the water does not begin to melt in the case of lamp-blaek. Water adsorbed in ts on the heat He found that | evolved when titative results he found no volved and the esuli. of experi- Parks' showed act with water levelopment of re centimeter of by lamp-black | — 85°. When juntil nearly 0° gelatinous pre- ecipitates may start melting at —20°. McIntosh and Edson? find that when a salt solution is plunged into liquid airy or solid earbon dioxide, the resulting solid forms a constant-m melting completely at the temperature at which thi have started freezing. It is not clear why this s| ADSORPTION OF SoLip By SoLtp Dried glue may he considered cither as a soli cooled liquid. If we consider it as a solid, then] of gelatine by glass is a case of adsorption of a Tt is more satisfactory to have cases where there 1 Meissner: Wied. Ann., 29, 114 (1886). 2 Phil. Mag. (6) 4, 247 (1902). 3 Jour. Am. Chem. Soc., 38, 588 (1916); 39, 627 (1917) 4 Ibid., 38, 613 (1916). elting mixture, solution should ould be so. or as a super- the adsorption solid by a solid. in be no doubt © 2010 Forgotten Books www. forgottenbooks. orgADSGRPTIO. but that both substances a: of rouge by metals.t. If a not kept sufficiently moist inctal surfaces that it can polish. Blue powder is a, have grains of zine coated when the zine is melted. coated with solid surface fi properties of the metals. OF LIQUID BY SOLID 79 e solids. We get marked adsorption etal is polished with rouge which is the rouge adheres so firmly to the not. be reinoved without spoiling the other case of adsorption. Here we with zine oxide which adheres even Aluminum and nickel are always ms which have marked effects on the Passive iron owes its peculiar proper- tics to the adsorption and stabilization of a higher oxide,? either FeO, or FeO;. Ij seems probable that vermilion is adsorbed by copper because De la Rue? says that electroplated copper blocks cause vermil not. lon to blacken while cast copper does We get what seems to b¢ a case of adsorption of a solid by 2, solid if we shake a modera' powder. Instcad of the fin oceupicd by the coarse pow ter.4 Tf the two powders coarser powder may be mas amount of the fine powder. sian blue was mixed with 1 sieve and did not pass a 1 ment the same amount off dolomite, all of which wol the first case, the powder v ely coarse powder with a much finer 1 powder filling the voids in the space ler, the former tends to coat the lat- we of different colors, the color of the ked completely by a relatively small In one experiment 0.032 g of Prus- 0 g¢ dolomite which passed a 40 mesh mesh sieve. In the second experi- Prussian blue was mixed with 10 g kd pass 1 200 mesh sieve. In the asa deep blue and in the second it was practically white, though the percentage compositions were the same in the two cases| Fe.03 colored the dolomite 200 mesh sieve and the dol When the dolomite passed did not pass a 100 mesh sie In a third set of experiment ened 10 g dolomite which w: dolomite was ground so tha * Drsew: Metallographic, 210) 2 Benner and Burnuam: Jo Mem. Chem. Soc. 2, 305 (1 ‘Finn: Jour. Phys. In another experiment 1 percent a full red when the rouge passed a lomite did not pass a 100 mesh sieve. a 200 mesh sieve and the iron oxide c, the powder was practically white. ts 8 milligrams of lamp-black black- s coarser than 40 mesh. When the t it all passed a 200 mesh sieve, 654 C1914}, ur. Phys, Chem., 21, 107 (1917). 45). hom., 21, 32 (1917); Braaas: Ibid., 28, 216 (1918). © 2010 Forgotten Books www. forgottenbooks. org8o APPLIED COLLOID CHEMISTRY inilligrams of lamp-black, or over cighty times as much, were needed to produce approximately the same tint. This behavior of powders is of great importance when using inert fillers in mixed paints! The ainount of barytes that can be mixed with colored pigments without injuring them is re~ inarkably Jarge. ‘There are hundreds of brands of para-red paints made and consumed every year by the agricultural imple- ment trade which contain as high as 90 percent of natural barytes. The opacity of paper may be increased by grinding the filler more finely. Fink has shown that a given mixture of a white non-conducting powder Like thovia with a black conducting powder like tungsten may either be black and conduct elcetricity or white and a non- conductor, depending on the relative coarseness of the two pow- ders. If one strews Lycopodium powder over thesurface of water and|then puts one’s finger into the water, the lyeopodium powder sticks to the finger and keeps it from being wettcd.* A coarse powder kept in a bottle will fall to the bottom of the bottle thraugh the foree of gravity while a very fine powder will stick to the walls of the bottle discoloring them. Writing on paper with a pencil or on a blackboard with chalk is a phenomenon of about the same type, though the matter is simplified by the roughened surface on which one writes. Sclid particles are rmb- bed) off and stick. It seems probable that the possibility of using face powder is merely a special case of a very fine powder adhering to a curved surface. n phosphate baking powders, the monocaleium phosphate is protected from moisture by an admixture of starch and it is well-known in the trade that the calcium phosphate must not. be too fine nor the starch too coarse; potato starch cannot be sub- stituted for corn starch, The retarding effect on the rate of setting of Portland cement, which is produced by the addition of gypsum is probably duc to the fact that the finer gypsum powder coals the coarser cement powder and acts to some extent as a protecting film. Tn all these cases the powders do not come in actual contact, but|are separated by a film of air which, however, holds them Toon: ‘Che Chemistry and Technology of Paints, 113, 138 (1916). Kunenpona and Scuunrae: Zcit. Kolloidchomio, 16. 183 (1914). me © 2010 Forgotten Books www.forgottenbooks. orgADSORPTION OF LIQUID BY SOLID 8L together, thus bdhaving like a liquid film. ‘Traces of moisture inercase the adhesion, as in the case of sugar and blueberries. The fine particles will be held more firmly in hollows in the coarser powders than on| projections and will therefore accumulate first in the concave portions, next on the plane surfaces, and last of all on the convex surfaces. Aitken! found that hot powders adhered +o a cold) rod of glass or metal; bué fell off when powder and rod were of the same temperature and were repelled when the rod was hotter than the powder. This is duc to a lowering of the surface tension of the condensed air film on the hotter side of the powder. It is necessary to work with such coarse particles that they fall off Under the influence of gravity except when special eonditions prevail. It has heen shown that the time factor is an important one in the wetting of some solids by some liquids, the air film being displaced slowly; It is possible that in some cases adhering powders displace |the air film slowly and become really adsorbed by the supporting solid. Apsorption oF Lrqurp py Liquip The spreading lof one liquid over another is usually considered +o depend on the relative surface tensions. If oil is dropped on. water, it is assumed that we have a water-air surface, a water- oi surface, and an oil-air surface as shown in Fig, 4.| If the surface ten- sion water-air is grcater than the sum of the surface tensions oil-water and oil-air, the drop of oil spreads out over the surface of the water. If the water-air surfaeg tension is less than the sum of the other two the oil Fis. 4. will draw up into a globule. While this may be a perfectly correct way of looking at things, it is not & useful one because Rayleigh? claims that three fluids eannot be in contact simultaneously. The simplest way to look at the AIR 1 Trans. Roy. So¢. Wdin.. 22. 239 (1884); Tasmtann: Drude’s Ann., 18, $56 (1905). ? Scientific Papers, 3, 354, 413, 416 (1902). 6 © 2010 Forgotten Books www.forgottenbooks. org82 APPLIED COLLOID CHEMISTRY matter is to consider the adsorption. If gil is adsorbed by water, it wets the water and spreads over the surface. Now the ad- sorbed layer may be very thin, not over 2a: in some cases. At greater thicknesses there is nothing to prevent the oil tearing loose from the oiled surface of the water and drawing up into drops under the influence of surface tension. This has been commented on by Rayleigh! and by Budgett.? The first portion of oil spreads over the water because it is ad- sorbed and held by the water. The second portion of oil flows out over the oiled surface, but is installe because the same mass of oil would have a, less surface if present|in drops and still more so if present in a single drop. The excess oil therefore draws up into one or more drops depending on conditions, thereby leaving bare oiled surfaces. The several drops will coalesce into one large one if brought in coutact.) If more oil is added the drops become larger and finally form solarge a drop that under the influence of gravity, it covers the whole surface of the water und becomes a Liquid layer of free oi!, From this way of looking at it, we sec that the phenomenon must |be gencral and so it is. Budgett* found that it was quite impossible to get a thin continu- ous film of kerosene or water on the surface of steel blocks. Microscopie examination showed that the applied films were not continuous membranes but that the liquid collected inio smull drops. This is undoubtedly exactly like Rayleigh’s ex- periment. On the surface of the wetted steel the kerosenc or water gathered in small drops. With different liquids, we should expect to find the drops first forming when the films reached different thicknesses. This has been noted by Hardy* who found that the thickness of the oil film varied from 2-200u« with dif- ferent oils. With one sample of oil therc was apparently no spreading at all. . If an oil is not adsorbed by water, there is theoretically a film of air between the water and the drop of oil, It seems improbable that this air film can continue to exist when a thick laycr of oil is present and yet, if not, there must be some point under some 1Seientific Papers, 3, 424 (1902). ? Proc, Ray. Soc., 86A, 30 (1911). 3 Ibid., 86A, 30 (1911). 4 Jbid., 86A, 612 (1912). © 2010 Forgotten Books www.forgottenbooks. orgADSORPTION OF LIQUID BY SOLID conditions when surfaces of oil, water, and air coexist. 83 Itseems probable that Rayleigh’s conclusion, that such a state of things cannot exist, holds only when the effect of gravity is ignored. With increasing amount of oil there probably comes a time when the air film is squeezed out entirely. ‘The breaking up of a liquid film into drops has been paralleled by the behavior of thin solid films when heated. Beitby' showed that a very thin film of gold leaf became granular if heated moderately. Apsorrrion or Sotrp sy Liquip A solid which is wetted by » Hquid, adheres to that liquid. With two liquids and one solid we get selective adsorption of the solid and this leads to some interesting results, which have been studied carefully by Hofmann.? If finely divided red lead is shaken with water and benzene or chloroform, the red lead ad- heres to the surface of the benzene or chloroform, making a practically continuous coating around the organic liquid pro- vided proper relative amounts of red lead and organic liquid are taken. The theory of the phenomenon has been given by Des Coudres.? The solid particles tend to go into the water phase if they adsorb water to the practical exclusion of the) other liquid; they tend to go into the other liquid phase if they tend to adsorb the other liquid to the practical exetusion of the|water; while the particles tend to go into the dineric interface in case the adsorption of the. two liquids is sufficiently intense to increase the miscibilhty of the two liquids very considerab face. between solid and liquid. at the sur- Of course the powder will only stay in the upper phase or the dineric interface in case it is so fine that the adsorption over- balances gravity. These conclusions as to the way a given pair of liquids will behave with a given solid refer to the relations pre- vailing under the conditions of the experiment.) Hofmann’s experiments with two liquid layers in glass test-tubes (soda-lime glass) showed that the time factor might be an important one. If a few cubic centimeters of an aqueous potassium bichromate 1 Proc. Roy. Soe., 72, 226 (1904). * Zeit, phys. Chom.,.83, 385 (1913), * Arch. Entwicklungsmechanik, 7, 325 (1898). © 2010 Forgotten Books www. forgottenbooks. org84 APPLIED COLLOID CHEMISTRY solution arp shaken up in a carefully cleaned glass test-tube, there remains on| the walls of the test-tube a continuous uniform coat- ing of solution recognizable by its yellow color. This film gradu- ally becomes thinner and paler but. does not break at any point until the water disappears completely through evaporation. Tf one adds a layer of xylene or kerosene to the aqueous bichro- mate solutibn in the test-tube, it is easy to see that there isa coating of aqueous solution between the organic liguid and the glass. If water is allowed to fow in at the bottom of the test-tube, the or- ganic liquid can be forced out at the top and there will be no sign of its |naving adhered to the glass wall at any point. If, however, the test-tube containing the aqueous bichromate solu- tion and tle xylene or kerosene be left standing quietly for a long time, 6-10 hours, it will be found that the organic liquid has diffused through the water film to some extent and now ad- heres to the glass wall nearly everywhere, having displaced the aqueous fie almost completely, If the contents of the test-tube are shaken |violently, the water displaces the organie liquid from the glass surface practically completely. The glass is therefore wetted wrod readily and more rapidly by water than by xylene or petroleuta; but a large mass of xylene or petroleum will gradu- ally displage a water film froin the glass surface. Qne would therefore expect to get a slightly different behavior with glass powder accprding as one treated it first with water o1 with organie liquid. This was exactly what Hofmann found. If the glass powder were treated first with water and then shaken with kero- sene, practically all the glass went into the water phase. If the glass powder were allowed to stand a long time with kerosene, or if it were heated with it to hasten the removal of the air film, some of the glass powder would remain in the dineric interface. Vig- orous shaking would, of course, cause the water to displace the kerosene. {Chloroform behaves towards glass and water some- what like xylene or kerosene though the tendency to displace the water layer from the glass is less than with kerosene. Small drops of chloroform do not break through the water film at all. With incredsing amounts of chloroform the force of gravity causes it to break| through at the bottom of the test-tube, the surface wetted by the chloroform increasing as the column of chloroform increases in height. © 2010 Forgotten Books www.forgottenbooks. org