146 ANALYTICA CHIMICA ACTA VOL.

2 (1948) THE ANILIC ACID NUMBER, AN ANALYTICAL INDEX FOR Cl3TING DLBASIC AClD ANHYDRIDES Anhydrides of dibasic acids in late years acquired great importance as raw materials for the preparation of synthetic resins and other plastic or plnsticising substances, and as a result there is now a most pressing need for a reliable and, if possible, simple method of testing these acid anhydrides, particularly in view of their king mixed with the corresponding free acids. Among the representatives of this group which are of greatest value for practical purposes may bc mentioned phthalic anhydride and its derivatives, as well as maleic anhydride and a series of products obtained by adding malcic anhydride to unsaturated organic compounds, either according to the principle of the diene synthesis (DIELS-ALDER reaction) or by substitutional addition. The method largely employed in analytical chemistry of plastics, according to the traditional analysis of fats and consisting in titrating the substance in alcoholic solution with potassium hydroside, cannot be used for determining the complete acid number (or to be more correct, saponification number) of dibasic acid anhydrides, because the latter immediately react with these alcohols to form semiesters. Besides, with such titrations we have often found the change-over poorly defined and the end point difficult to establish, presumably because the resulting semi-esters easily saponify. There is also the fact, at any rate according to our own experience, that the conversion of dibasic acid anhydrides to semi-esters is by no means always cluantitatively complete, so that when titrating in ethanol one should not expect that exactly one half of the value corresponding to the amount of anhydride present will be titrated in every case. In a publication entitled T/le cstcrificntiort rate of &basic mid ndzyclrides with j~i?rrnry ahohoh nt YOO?U temperature, SIEGEL AND h~OItAN recently recommended the reaction between alcohols and anhydrides of dibasic acids, especially phthalic and maleic anhydride, as a basis for the analytical determination of these anhydrides in mixtures with the corresponding free acids. Without enlarging here upon Iteferemes p. rqg. VOL. 2 (1948) THE ANILIC ACID NUSlBER I47 the merits of this method of analysis, we would mention that for the reasons explained above we ourselves experienced a host of difficulties in our efforts to obtain reliable results on the same principle when analysing various dibasic acid anhydrides. We therefore sought a better method, which we believe we have found on the following basis. It is a well-known fact that phthalic anhydride and other anhydrides of dibasic acids may, according to the experimental conditions, react with aniline to form either an anil or an amlic acid, thus: Cd-J, + H,N. C,,I-I ,, - C,H,&XP. 0 C,I I 6 + Hz0 Which of these reactions (condensation or addition) will take place dcpencls largely upon the solvent in which the components arc brought together. In all the cases we have examined, aniline in acetone is added quantitatively to the dibasic acid anhydride to form the corresponding anilic acid. The titration of this acid is effected without difficulty even in the presence of an excess of aniline. We consider this a better method than the titration of semiesters because the convcrsron of the anhydrides to the corresponding anilic acids takes place quantitatively under conditions whrch we have worked out in detail, after which, when titrating the anilic acids, the end point is characterized by a sharply defined easily observable change-over. In this way, of course, only one of the two carboxyl groups on which the dibasic acid anhydrides are based undergoes titration; the other is ncutralised as an anilide. The index found in this way is referred to as the anilic acid mmtDer. We consider that this constant may be a useful criterion for testing the raw materials mentioned. Chemically pure dibasic acid anhyclrides will yield the theoretical values for the

anilic acid number. But if a dibasic acid anhydride contains as an impurity free dibasic acid (or other carbosylic acids), higher values wilA he found for the anilic acid number. Under the conditions given these impurities invariably react with aniline to form a salt, which has no influence, however, upon the results of titration. When we know for certain that we are only dealing wrth a mixture of an anhydride and its free dibasic acid, the content of thcsc two components can easily be determined from the difference between the calculated and the titrated value of the anilic acid number. This applies to such mixtures in all proportions. After we had found out this method and successfully applied it for some time, we discovered that the reaction between acetic anhydride and aniline was utilized by MENSCHUTKIN AND WASSILIEF~ more than half a century ago for the titration Re/ererlccs p. r-/g. 148 C. P. A. I<APPDLMEIER, W. R. VAN GOOR VOL. 2 (1948) of mixtures of acetic acid and its anhydride in an aqueous solution of aniline. In this case there is of course no question of forming an anilic acid and the conditions arc quite different from those obtained with the method worked out by us. The latter will, however, serve equally well for the testing of acetic anhydride. EXPERIMENTAL DATA An amount of 0.5 to I g of the substance is accurately weighed out and dissolved in approximately 5 ml of pure acetone, whereupon about 5 ml of pure aniline is added. In the case of dibasic acid anhydrides with a considerably greater molecular weight than phthalic anhydride, mnleic anhydride, etc., a proportionately larger weight of substance should be taken. Sometimes a crystalline precipitate of the anilic acid is at once produced, as for instance with tetrachloro-phthalic anhydride and often also with maleic anhydride. This does not, however, interfere with the determination of the anilic acid number. With the low-molecular acid anhydrides mentioned the addition of aniline gives a spontaneous and quantitative result. Aft.er all the components have been well mixed, titration is at once effected with 0.5 N-alcoholic potassium hydroxide on phenolphthalein, the anilic acid number being calculated in the same way as normal acid numbers. In the case of acid anhydrides with an appreciably higher molecular weight, e.g., the products obtained by the addition of malcic anhydride to drying oils, the mixture is first boiled for half an hour under reflux and, having been cooled down, is titrated at room temperature. It goes without saying that for all these determinations the acetone and aniline should be chemically pure and pcrfcctly neutral on phcnolphtalcin. I Anillc acid number Phtld~c nnhydrlclc . . . . . . . . 378.4 Tctrnchloro-plltli,lllL anhyclridc . . . 195.8 Succimc anhytlr~clc . . . . * . . 560.0 Malclc nnhyclridc . . . . . . . . 57X.4 Rdcl~tlon product 01 m.llclc .~rihydrx_ic to lmscccl 011 121 Aclclitlon product of inalclc .Inhytlritlc to l~nsccd 011 93 -II 378 379 196 197 560 561 571 572 I22 125 92 88 In determining the anilic acid number of the so-called maleic treated oils (the last two examples in the above table), the results found do not tally so neatly Referewes p. 149. VOL. 2 (1948) THE ANILIC ACID NUMBER =49

with the calculated values as is the case with chemically pure anhydrides. They are, however, undoubtedly of practical value for investigations in this line. When calculating the anilic acid number for these products on the basis of titration one must of course take into account the acid number of the original linseed oil. SUM3lARY For tchtlng the purity of d~b.lsm nc~tl anhydrults and for nnolyslng mixtures of thcsc anhydrrdcs wrth the corrcsponclln~ free nerds the dctcrmlnatlon of rl new rnclcx number IS rccommcnclcd, rndrcntcd as tlic nnillc acid number. The proccs IS bnscd on the fnct that thcsc acid anhydridcs, when dlssolvcd In ncctonc. under surtnblc cxpcrlmcntal condttlons can bc added rcadrly and quantltatlvcly to .mrllnc with rcsultrng formation of tl~c corrcspondmfi antlrc nctds. Immcdiatcly nftcr addition. titration IS cffcctcd with .rlcoliolic pnt,usslum hydroxrdc on phcnolphthnlcln. Pure dlbnslc acid anhytlrlclrs In tills cnsc yrclcl tllc c:~lcul.~tcd nmlic ncnl number. In the prcscncc of free acids tbc vnlucs found arc too high. Tl~c free nclcl content can bc caslly dctcrmrncd from the dlffcrcncc bctwccn the thcorctlcal and the found .lmllc acid riumbcr. Pour 14prcuvc tic la purctb dcs .tnhydridcs tlac~dcs dnzarboxylrqucs nmsi quc pour lannlysc rlcs mblangcs de ccs nnhydrnlcs dacidcs .a~c Its ncrdcs llbrcs corrcspondnnts, on recommnndc In dktcrmlnatlon dun nouvcl rndlcc cnrnctcrlstrquc nuqucl on a donnb lc nom dlndnzc dncidc dnnilc. Cc procCd6 rcposc sur Ic fait quc, clans dcs condrtions clcssni convcnablcs, ccs anhytlrnlcs dacldcs d15sous dons 1acGtonc. Iwuvcnt sndditlonncr facrlcmcnt ct quantitativcmcnt a l.tnllrnc cn formant h-3 nciclcs dnnilc corrcspondants. Imm6dnttcmcnt aprcs laddltlon, on titrc h la lcsslvc dc potassc alcoollquc cn prkscncc de phenolphtal6lnc. Des anhydrldcs dacnlcs dicarboxyllqucs purs donncnt nlors lrndlcc clac~dc danilc cnlcul& En prcscncc d.~cx_lc librc. lcs vnlcurs obtcnucs sont trap 6lcvks. La tcncur en acnlc llbrc pcut Ctrc cnlculcc facllcmcnt dc la tl~ffkcncc dc4 vnlcurn th&orrqucs ct trouvks dc llnclicc dnciclc danilc ZUSARIRIENFASSUNG Firr c11c licrnhcltsprufung tlcr Anhydrldc von Dilcarbonsaurcn. SOWIC: fur tllc Analyst von Mischungcn drcscr Saurcanhydrldc mlt den Ihncn zu Gruntlc Ilcgcndcn frcien Saurcn, wlrd dlu Bcstimmung cmcr ncucn Kcnnznhl cmpfohlcn, dlc mtt dcm Namcn Anils&urcz,thl bczcichnct wird. D.IS Verfahrcn bcruht darauf. dass d~csc Saurcanhydrldc untcr gcclgnctcn Vcrsuchsbedingun~ en, In Accton gcldst. lcicht und qunntltatlv Anllm 2~1 nddicrcn vcrmogcn, untcr B1ldung dcr cntsprechcndcn Amlsaurcn. Sofort nach crfolgtcr Addition wircl m1t nlkoholischcr Knl1lnugc a;f Phcnolphthnlcin titncrt. Rctnc D1karbonsaureanhydrIdc crgcbcn dabc1 die crrcchnctc Amlsaurczahl. Bc1 Anwcscnhclt frcicr Snore wcrdcn zu hohc Wcrtc gcfundcn. Aus dcr Dlffcrcnz zw1schcn dcr thcorct1schcn und rlcr gcfuntlcncn Anilsaurcmhl Iassst 51ch le1cht clcr Gchalt on frclcr Siurc crrcchncn. REFERENCES 1 E. F. SIEGT.L AND M. K. hIoRAN, J. Anr. C/J. .5x., 6g (1947) 1457. 2 MENSC~IUTKIN AND \VAS~ILIEP, J. Russ. P~JYS. Clr. Sot.. 21 (x889) rgz. Received November 25th, 1947