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Liquid chlorine as an ionizing solvent. The conductivity of oxonium compounds in liquid chlorine Mennie, John H. 1920

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LIQUID CHLORINE a s an IONIZING- SOLVENT. The CONDUCTIVITY of OXONIUM COMPOUNDS i n LIQUID CHLORINE. THESIS submitted as part of the requirements for the degree of Master of Arts in the University of British Columbia by John H. Mennie, B.A. University of British Columbia Department of Chemistry 1920. I , In the course of an investigation of some of the physical properties of liquid chlorine, Johnson and Mcintosh examined it as an ionizing solvent and failed to find any inorganic substance which was ionised in it. The y observed that solutions of certain organic compounds containing oxygen, such as alcohols, ethers, ketones and esters, which themselves gave no evidence of ionization, immediately began to conduct when a small quantity of HG1 was added. These substances, when dissolved in chlorine, form 2 compounds of the general type EtherxCl~, wliich are apparently not ionized.' Plotniko v foun d that ether dissolved in bromine gave a conducting solution but this was probably due to the 4 formation of small amounts of HBr. Wit h the halogen acids 5 compounds of the type Ether HC1 ar e formed and these conduct 6 X  Y very well . Transpor t number determinations have shown that the ether is carried to the cathode, indicating that it forms 7 part of a positively charged ion. Johnso n and Mcintosh concluded that the conductivity which they observed was due to •the ionization of these compounds. 1. J o u r . ' A m . ' Chem.! S o c 31 : 1138 (1909). 2 . D* Mcintosh: Jour.1 Chem.' Soc. 87: 784 (1905). Jour . Am.: Chem.' Soc.1 33: 71 (1911). 3 . Z e i t . Phys.' Chem. 4 - 502 (1906). . . --4. Johnson and Mcintosh: loc. ; c i t . page 1144. 5. Archibald and Mcintosh : Jour. ' Chem.1 S o c ' 85: 919 (1904). 6. S t e e l e , Mcintosh and Archibald: P h i l . Trans.. A-205: 99 (1905^ Archibald: Jour . Am.1 Chem.1 Soc. 29: 665 (1907). Maass and Mcintosh: Jour. : Am.' Chem.1 Soc. 35: 535 (1913). 7. S t e e l e , Mcintosh and Archibald: l o c . c i t . 2 c The present investigation consists of a repetition of Jolmson and ITcIntoshfs qualitative tests and a quantitative study of the change in conductivity of solutions of the Ether-Chlorine type with addition of HC1. QUALITATIVE RESULTS. Conductivities were measured by the Kohlrausch method using a slide-wire bridge of ordinary type. Th e conductivity cell was a small glass tube with sealed-in electrodes. Abou t 4 -6 ccs . of chlorine was used. Th e cell was kept in a bath of ether and solid carbon dioxide, which gives a fairly constant temperature of -80°C. Th e chlorine was made by dropping hydrochloric acid on potassium permanganate, was passed through wash-bottles containing water and concentrated sulphuric acid and was dried with phosphorous pentoxide. Th e mean of a number of measurements L gave a value of 0.07 X  10 fo r its conduct!vity but with such a high resistance it was impossible to determine the minimum with any degree of accuracy. Tests were made with about 180 inorganic compounds, including various salts of all the common metals, and such substances as water, hydrogen chloride, hydrogen sulphide, tin tetrachloride, bromine, etc. Abou t 80 organic compounds were also tested, including hydrocarbons, alcohols, ketones, aldehydes, esters, acids, amines, nitrilcs, etc. I n no case HCl gas, generated by the action of sulphuric acid on sodium chloride and dried with phosphorous pentoidde, was then bubbled through solutions of pentane, acetic acid, aldehyde, ethylamine, ether, alcohol, ethyl acetate and acetone. Th e first four showed no evidence of ionization but the last four gave conducting solutions* QUANTITATIVE MEASUREMENTS. The conductivity apparatus used was the same as in the previous work but the conductivity vessel was graduated so that the volume of chlorine used in each experiment could be read.1 Th e cell constant, determined by means of N/50 KOI at 25°C, was found to be 0.4872. Pou r or five ccs. of chlorine were introduced into the cell, the volume read, and the weight calculated from the value for the density given by i Johnson and Mcintosh. A  weighed amount of solute was added from a pycnometer." HC l gas was then slowly Jhassed in from a small gas burette with levelling tube containing mercury? Th e mercury was protected from the action of the HCl by a layer of concentrated sulphuric acid. Th e gas was introduced through a capillary tube leading to the bottom of the cell and after each addition of gas, the Dewar flask containing the cell was lowered sufficiently to remove the capillary tube from the liquid while measurements were being made.1 Reading s of conductivity were taken at regular intervals until the value became constant. I t was found that after each addition of 1. loe . cit. 4. HC1 i t took some t ime f o r a c o n s t a n t v a l u e to bo r e a c h e d . This t ime was a s much a s one o r two hours f o r t h e f i r s t few a d d i t i o n s of g a s , a f t e r which i t g r a d u a l l y d e c r e a s e d t o t e n o r f i f t e e n m i n u t e s . The change w i t h t ime was i n v a r i a b l y a s t e a d y i n c r e a s e excep t i n t h e case of t h e t o l u o l s o l u t i o n d e s c r i b e d l a t e r and f o r a s m a l l p a r t of tho a l c o h o l c u r v e . ETHER - CHLORINE - HC1. The e t h e r used was some which had been k e p t f o r s e v e r a l months over sodium. The v a l u e s o b t a i n e d a r e shown i n Table 1 and i n P i g . 1, Curve I . I t was obse rved t h a t i f on ly a s m a l l q u a n t i t y of e t h e r (1 - 2 %)  was d i s s o l v e d i n t h e c h l o r i n e no a p p r e c i a b l e c o n d u c t i v i t y was o b t a i n e d even on t h e a d d i t i o n of four or f i v e t imes t h e mo lecu l a r e q u i v a l e n t of HC1. I f t h e c o n d u c t i v i t y i s a t t r i b u t e d to t h e Ether-HCl compound, a p p a r e n t l y t h e e q u i l i b r i u m r e l a t i o n s of t h e system a r e such t h a t none of t i l l s compound i s formed u n t i l t h e e t h e r c o n c e n t r a t i o n r e a c h e s a c e r t a i n v a l u e . ALCOHOL - CHLORINE - HC1. The a l c o h o l used was U a l l i n c k r o d t ' s " a b s o l u t e " and was d r i e d over anhydrous copper s u l p h a t e . The v a l u e s a r e shown i n Table 2 and F i g . 2« I t w i l l b e s een t h a t t hey a r e ve ry much lower t han i n t h e ca se of t h e o t h e r s o l u t e s u sed . The c o n d u c t i v i t y i n c r e a s e s ve ry r a p i d l y up to a c o n c e n t r a t i o n of abou t 20^ HC1 and t h e n d rops sudden ly t h e n g r a d u a l l y and s t e a d i l y i n c r e a s e s . S t e e l e , Mcintosh and A r c h i b a l d have 1. l o c . c i t . : . TABLE 1. Weight of Chlorine - 7.70 gns . Weight of Ether - 1.1630 gno. Total HC1 added. Molecular p ropor t ion Conductivity __ -0.0460 0,0925 0.1396 0.1844 0.2316 0.2780 0.3258 0.3723 0.4189 0.4653 0.5119 0.5582 0.6032 0.6491 0.6949 0.7408 0.7764 0.8236 0.8623 0.9073 0.9526 0.9981 HCl/Ether 0.080 0.161 0.243 0.321 0.403 0.484 0.566 0.649 0.730 0.810 0.890 0.973 1.05 1.13 1.21 1.29 1.35 1.43 1.50 1.58 1.66 1.74 x 10 " 0.039 0.142 1.188 3.17 3.49 5.65 5.67 7.78 8.39 9.15 9.88 10.75 11.20 12.06 12.45 13.28 13.86 13.80 13.86 14.65 14.26 D, 0.5 ~ . shown that the halogen acid compounds aro probably polymerized in solution so tills peculiar change in the conductivity may be attributed to variation with the HCl concentration of the relative rates of association and dissociation. ACETONE - CHLORINE - HCl. The acetone used was made by Merck. Th e values obtained are shown in Table 3 and Pig. 3, Curve I. Th e curve is similar to that obtained with ether. I t was noticed, on removing the conductivity cell at the conclusion of tho experiment, that the liquid had separated into two distinct layers* Thes e differed only very slightly in color but when mixed by shaking, separated again in a few moments. Th e constitution of these layers is a question tfor further investigation.' ETHYL ACETATE - CHLORINE - HCl. The ethyl acetate used was shaken with water to remove the alcohol, dried over calcium chloride and redistilled. Th e values obtained are shown In Tabic 4 and Pig. 1, Curve II. Th e curve resembles those obtained with ether and acetone. A s with ether, a fairly large proportion of ethyl acetate seemed necessary to give a conducting solution.1 A  solution containing about 6f»  ethyl acetate was only beginning to show an increase in conductivity when about one molecular equivalent of HCl had been added. TfelGht of Ch lo r ine Weight of Alcohol T o t a l HC1 added . 0 .0168 0 .0326 0 .0454 0.0614 0.0774 0 .0922 0.1088 0.1241 0.1382 0 .1628 0 .1849 0 ,2306 0.2762 0 .3226 0.3682 0 .4133 0 .45S3 0 .5035 0 ,5475 0.5920 O.6366 0.6824 0 .7257 0 .7705 0 .8152 TABLE 2 . - 8 .21 - 0.3784 Cna. gme. H o l o c u l a r p r o p o r t i o n B01/A1 0 .056 0 .109 0.151 0 .204 0 .258 0 .307 0 .362 0 .414 0 .460 0.541 0.615 C."53 0 .920 1.08 1.23 1.38 U 5 3 1.573 1.82 1.97 2 .12 2 .27 2 .42 2 .57 2 .72 C o n d u c t i v i t y x 1 0 " ' 0 .037 0 .224 0 .475 0 .521 0 .630 0 .332 0 .326 0 .358 0 .402 0 .455 0 .525 0.540 0 .598 0 .652 0 .704 0.760 0.712 0 .744 0 .763 0 .787 0 .810 0 .847 0 .970 0 .997 $•03 M F ; ! 4-i"""; 72C-"jltnyljAlcobol - Chlo fino :-:c Cdnduc ! J L Ivit-; !iri i i j 0.9 0.$ 0.7 O.o 0 .3 0.4 0 .3 0 .2 i_jj i_ i t - 4 -J j 1 1 - 1 J ! 1 - *  ! 1 L. + ?Xoloculitr ^rooor *lon H 10. TABLE 3 . Weight of Chlorine -  6.2 6 gms . Weight of Acetone -  0.451 5 gms . Total HC1 added 0.0238 0,0462 0.0920 0.1363 0.1813 0.2254 0.2700 0.3147 0.3579 0.4025 0.4467 0.4906 0.5352 0.5808 0.6249 0.6686 Molecular proportion HCl/Acetone 0.084 0.163 0.324 0.482 0.640 0.795 0.952 1.11 1.26 1.42 1.57 1.73 1.89 2.05 2.20 2.35 Conductivity 0.0125 0.028 0.383 0.904 1.78 3.88 6.98 9.58 11.3 12.4 13.8 14.75 16.8 "17.54 18.0 18,75 FT - -  -!-.. :it: ' ' -'r. i b; it ; ::-: I IW- •-  -:;''1'. mP U. ...>'. ' . . 1 li»fsf -^ ' .......|... : , ;.| :;:.;... . U . •;.fv " " : - , : • 0.5 1. 0 1.5 2 .0 2,5 12. TABLE 4 . Weight of Chlorine -  8.2 1 gns . Weight of Ethyl Acetate -  1.065 1 gms. ; Total HC1 added Molecula r orooortion Conductivit y ---- HCl/Ethy l Acetate .  x  10"5" 0.0447 0.0839 0.1334 0.1781 0.2234 0.2685 0.3131 0.3570 0.4016 0.4461 0.4909 0.5352 0.5790 0.6240 0.6682 0.7118 0.7548 0.7958 0.8376 0.8011 0.9247 0.9667 1.0096 0.101 0.201 0.302 0.403 0.505 0.608 0.709 0.808 0.910 1.01 1.11 1.21 1.31 1.41 1.51 1.61 1.71 1.80 1.90 2.00 2.09 2.19 2.27 • • ^ a S 0.007 0.013 0.042 0.140 0.675 1.81 3.12 4.84 7.60 9.40 11.30 12.90 14.5 16.0 17.7 19.25 20.8 22.0 23.0 23.8 25.3 26.0 13. ACETOHE - TOLUOL - HCl. The question suggests itself, does the chlorine actually play an active part in the ionization of these solutions or is the observed conductivity due to the ether and HCl alone, the chlorine serving only to dilute the solution? To throw some light on this problem, a series of measurements was made using toluol in place of chlorine. Toluo l was selected as a solvent unlikely to enter into combination or exercise any ionizing effect. Th e toluol used was freed from water, etc.!, by cooling it in the ether - carbon dio:dLde bath and filtering several times through asbestos, until it no longer appeared turbid at that temperature. Aceton e was used as the solute, approximately the same quantities being used as in the case of the acetone-chlorine measurements. Th e results are shown in Table 5 and Fig. 3, Curve II. It may be seen from the graph that there is no similarity between the behaviour of the chlorine and the toluol solutions. Th e values for the conductivity are much smaller in the latter case. A  sharp break in the curve occurs at the concentration equivalent to C,HgO.HCl. Th e curve in 4 this respect resembles those obtained by Haass and Mcintosh for methyl and ethyl ethers in HCl alone.' Moreover, instead of a gradual increase in conductivity with time, after each addition of HCl, there was an immediate increase, followed bj a gradual and slight decrease to a steady value. 1. loc 1 cit.1 14. TABLE 5. Amount of t o l u o l - 4 ,6 ccs . Weight of Acetone - 0.5770 gms. Total HC1 added 0.0462 0.0922 0.1384 0.1846 0.2299 0.2749 0.3201 0.3651 0.4067 0.4512 0.4962 0.5416 0.5870 0.6321 0.6775 0.7231 ' 0.7685 Molecular proportion HCl/Acetone 0.127 0.254 0.381 0.508 0.613 0.757 0.882 1.00 1.12 1.24 1.37 1.49 1.62 1.74 1.87 1.99 2.11 Conduct! vitjr x 10""5"' 0.031 0.091 0.274 0.728 1.20 1.47 0.958 1.29 1.90 2.45 3.00 3.77 4.50 4.97 5.70 15. These facts seem to indicate that the chlorine plays an active part in the ionization of the solution. I f ionization i s accompanied by combination between solute and solvent^ a compound containing both chlorine and hydrochloric acid must be formed. SUMMARY. 1, Th e properties of liquid chlorine as an ionising solvent have been examined and the observations of Johnson and Mcintosh confirmed. N o inorganic substance was found which is ionized in tills solvent and none of the ordinary organic compounds. Ether , alcohol, acetone and ethyl acetate were found to form conducting solutions when HG1 was added to the solution. 2. Th e change in conductivity with increase in HC1 concentration, of the last-named solutions, has been measured. A  gradual increase of conductivity was observed as far as the measurements were carried. Alcoho l proved to be an exceptional case. A  rapid increase followed by >a sudden drop and then a gradual increase, was observed. A s the conducting substance is probably polymerized in solution, this variation in the conductivity may be attributed to a variation with concentration of the hydrochloric acid, of the relative rates of association and dissociation.' 1. Steele , Mcintosh and Archibald: loc. cit. 16. 3« Th e conductivity of a solution of acetone, with toluol substituted for the chlorine, was measured under similar conditions. Th e conductivity was very much less than In the case of the corresponding chlorine solution and the shape of the curve was entirely different, resembling that obtained by Maass and Ilclntosh for ether in liquid HCl alone. It is concluded that the chlorine takes part in the ionization and compounds containing both hydrochloric acid and bhlorine are probably formed. Chemistry laboratory, University of British Columbia, Vancouver, B.C. 

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