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Anew Scale of Basicity in Oxide Slag and the Basicity of the Slag Containing Amphoteric Oxides *

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Anew Scale of Basicity in Oxide Slag and the Basicity of the Slag Containing Amphoteric Oxides * ANew Scale of Basicity in Oxide Slag and the Basicity of the Slag Containing Amphoteric Oxides * By K azumi Mori * * systems. According to this definition, an "acid" I. Introduction is either a donor of protons (0 1' cations) or an The acidic or basic beh avior of s lag-forming acceptor of electrons (or anions), while a "base" oxides a nd the basicity of slag have a n important is either a donor of electrons (or a nions) or an bearing on the iroll- a nd steel-making processes. acceptor of protons (or cations) . Based on this In most cases some ratio of the amounts of basic theory, a definition of acid-base for oxid e a nd slag oxides to those of acidic oxides has been used as systems may be m ade as follows: A basic oxide a measure of basicity, but it is only an empirical is one that can donate oxygen ions, whi le an acidic measure a nd cannot be cons ider ed a rea l measure oxide is one t hat can accept oxygen ions from of chemical properties. Moreover, in the expr e'­ bas ic ox id es. Such a definition has a lready been s ion of s lag basicity little attent ion has been pa id made wit h glass systems by Sun and SilvermanC,)G) to the behavior of a mphoteric oxides such as AI "O" and wit h slag syst ems by Chi pma n a nd Chang/)_ a nd TiO". Thus, defining and measuring the slag On t he basis of t his definiti on, it is po sible to basicity in a theoretically satisfactory manner has expr eo: s t he scale of basicity or acidity for p ure been an unsolved problem. It is from t his aspect oxides by the strength of the metal-oxygen (M-O ) that the a uthor has an interest in the s ubject. bond. Sun,n) X) us ing thej'mal data, estimated the In the present repor t a new scale of bas ic ity is r elative M-O bond strength, which he identified given, based on the fact that t he ratio of ferric with t he scale of basicity or acidity of oxides. An to t otal iron (F e:l+/ L:Fe) in ox ide s lag is greatly analogous sca le may be expressed by t he binding affected by the change in bas icity, together with energy between a cation a nd an oxygen ion r epre­ the method of experimenta l determination of the sented by: basicity valu es and the r esults of the study on I = 2 z/a2 slag containing amphoteric oxides. where z is the cha rge of the cation and Cl is the II. General Rev iew of the Slag Bas icity dis tance between the cation and the oxygen ion. The most conventional expression of s lag basi­ The larger I val ue an ox ide has, the stronger is city, which is implied as the strength of base in its acidic prope rty ( 01' t he weaker its basic pro­ the s lag, has been 11= CO ~ CaO) Co;, Si0 2 ) or \" pe rty). The experimental value of acid-base = L: (0;, base) / L: (";, acid ). In some cases in the str engt h of oxides could be obtained f rom t he V' ratio some factors relating to the r elative acid­ coloring transition point in glass or f rom the mea­ base strength of the oxides were given in the s urement of e. m.f. in t he cell where molten g lass weight percentage.! )~) "Excess base" expr essed by was used as the electrolyte.!) Grant and Chipman';) or the "concentration of free Thu" based on the fundamental definition by oxygen ions" devised by H erasymenko a nd Speight4 ) Usanovich, the definite concept for t he bas icity of could also be used as the expression of s lag basi­ pure cxides has bee n well establis hed. However, city. The common factors in these expl'essions of t his idea of basicity has not been taken into con­ s lag basicity a re that the constituent oxides were sideration in the conventional expr ession of bas icity c lassified distinctly either as acidic 0 1' as basic and in mu lticomponent systems. It is t he chief object that based on this classification the bas icity value of this paper to give a new scale of basicity w h ich was calculated in an a rithmetical ma nner from is able to deal with pure oxides as well as multi­ s lag analyses. However, s ince s uch a procedure component oxide systems on t he same ground. to express s lag basicity is not based on theoretical a rguments, it is difficult to understand what is im­ I I I. A New Scale of Bas icity and Its Measure­ plied theoretically by the basicity thus expressed. ments On the other hand, in t he purely fundamental I. A New Scale of Basicity fie ld of physica l chemistry, various definitions have been given to the concept of acid and base Because oxide s lag contains large amounts of by Arrhenius, Germann, Bronsted, Lewis, Usano­ oxygen ions, it seems most r easonable to express vich a nd BjelTum. Of these definitions, Usanovich's the slag bas ic ity by the oxygen-ion activity. definition is most easily applied to oxide a nd slag The oxygen-ion activity may be obtained f r om t h e measurement of e.m.f. by the methods developed by Lux!") a nd Didtschenko and Rochow. !) How­ * Lect ure delivered before the 53 rd & 55 th Grand Lecture Meeting April 1957, 19 58 in Tokyo. Tetsu-to-Hagane ever, the measurement on general s lag systems will (Journal, Iron & Steel Institute, Japan ) Vo l. 46, No. 4 be extremely difficult. pp. 466--473 It is well-known that the ratio of ferric to total * * Assistant Professor, Department of Metallurgy, Faculty ir on (F e+ 3/ L:Fe) in oxide s lag is increased w ith of Eng ineering, Ibaraki University. increase of the basicity of a dded slag under con- 25 11 stant oxygen pressure. )- I:l) This phen omenon I. Platinum wire ..,. -------- ---1 might be derived from the fact that the iron ratio 2. Rubber tublnJ: is aff ected by the compound strengt h of M-O bonds 3. Pinch cock r elating to the constituent cations other than ferric 4, Gil S in let and ferrous ions. Since, as described in the pre­ S. !'t·Pt. Rh thermocouple vious section, the M-O bond strength itself is the 6. As bestos head scale of basicity for pure oxides, this phenomenon 7. Nicke l plate for radiation has been chosen in t he present pa per to meas ure shie ld t he bas icity of slag, as was s uggested by La rson 8. Gland for rubber packing a nd Chipman.!'!) 9. Water-c ooling tube 10. Semi·sinter corundum tu b,: Since oxygen ions a r e common to a ll the com­ 10 -'- --- - -- - II . Ere ma hea l ing e lement s ponents in an ox id e s lag syst em, it is adequate to ~ - --- --- ------- ---II 12. Iso Ji le board Li se ionic f l'action of cation s in the expressions of 11--- ---1----- - ---1 2 13. A lu ndum board --- 13 the concentration of the added s lag, of which the 14 . Alumina tu be basicity is to be determined. Then the concentra­ 15. Thermocouple protection 15 - - - - - - - -- - - - --- - - -14 tion of the added s lag ( C ) is represented by the tube 17 - --- -- - -- expression: 16. Platinum crucible --- 16 18 -- - - - ..... • 17 . Alum ina C = LM / (LFe + LM) (1 ) 18. Chamotle -- - 19 LFe = Fe2+ + Fe:l+ 19. Alundum tune LM = Ca2+ + SiH + Ti4 + Al:l+ + 20. S tee l plate 21. Water·cooled Since in general the ratio: \('sse l ( 2 ) 22. Gas outlet.. cha nges with C, it is not adequate to choose r at some concentration as the scale of basicity. There­ fore, the gradient of an roC c urve at the infinitely dilute concentration, or (dr / dC)c 0' was ch osen as the scale of basicity. In t h e concentration ra nge where r cha nges linearly with C, (dr/dC)c 0 m ay be put in t he following form: Fig. 1 Experimental furnace (dr / d C)c -0 = (r - ro ) / C ( 3 ) which is independent of e. H er e i'" r epresents t he in Fig. 1. The h eating element cons isted of s ix r of t he pure iron oxide. Erema rods (SiC) . A long the center of the fur­ According to the study by La rson a nd Chi p­ nace was a semi-sinter co rundum tube. A sm all man,I :!) a linear relations hip between rand C seems p latinum crucible with a capacity of 1 cc was to be approximately establi s hed below 20-25 m ol";, s Li spended on a platinum wi re inside the tube. In of the added s lag. In t he present study, based on t his crucibl e 1. 5 g sample was melted. t he ass umption of linear relationship between r Samples were prepared by mix ing fe rrous oxide a nd C, the scale of basicity is given by the equa­ with the slag whose bas icity is to be determined. tion: F errous oxide material was made by melting ferric B = ((r - r o) / C) x 10 ( 4 ) oxide reagent in an iron crucible.
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