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Lawrence Berkeley National Laboratory Recent Work Lawrence Berkeley National Laboratory Recent Work Title IONIZATION OF STRONG ELECTROLYTES XI. THE MOLECULAR STATES OF NITRIC ACID AND PERCHLORIC ACID Permalink https://escholarship.org/uc/item/03s339xt Authors Redlich, O. Duerst, R.W. Merbach, A. Publication Date 1968 eScholarship.org Powered by the California Digital Library University of California UCRL-18049 University of California Ernest O. Lawrence Radiation Laboratory IONIZATION OF STRONG. ELECTROLYTES Xl. THE MOLECULAR STATES OF NITRIC ACID AND PERCHLORIC ACID O. Redlich, R. W. Duerst and A. Merbach January 1968 TWO-WEEK LOAN COpy This is a library Circulating Copy which may be borrowed for two weeks. For a personal retention copy, call Tech. Info. Dioision, Ext. 5545 DISCLAIMER This document was prepared as an account of work sponsored by the United States Government. While this document is believed to contain correct information, neither the United States Government nor any agency thereof, nor the Regents of the University of California, nor any of their employees, makes any warranty, express or implied, or assumes any legal responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by its trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof, or the Regents of the University of Califomia~ The views and opinions of authors expressed herein do not necessarily sJate or _ reflect those of the United States Government or any agency thereof or the Regents of the University of California. ~. '; . Submitted to Journal of Chemical PhYsics 'UCRL-18049 .' '" " , I)reprint 1 ", ':" ': .. .," ~~: . ~, , . ~ ,'. i ~'. • ;.;. '•. : ...... ~. ' : .~' .. : .' . ':.'," .. '. ~ -, . '. "', , '. ... ".' : .. < .," . ':' ..:: " ,:. , , , , "," '. '/ . ' '., UNIVERSrry OF CALIFORNIA ' .. ",', Lawrence Radiation Laboratory', Berkeley, California '.,' T' '. ;.' <.;, .• :'., , ' AEC Contract W-7405-eng-48 . \,' -- " " .' ~' .' ; "', . , " :' ' . ". ~ . ,. :' " .," .... " ' . ' , ' .. ' IONIZATION OF STRONG ELECTROLYTES XI. THE MOLECULAR STATES OF NrrRIC ACID AND PERCHLORIC 'ACID O. Red'lich, R. W. 'Duerst, and A. Merbach January 1968 , , .~, , . \ ..... UCRL-18049 1.: ' : ..... J . t'.' " . '.' ..... , . ,".' "', .... , . IONIZATION OF STRONG ELECTROLYTES XI. THE MOLECULAR STATES OF NITRIC· ACID AND PERCHLORIC ACID . o. Redlich~ R. W. Duerst*'and A. Merbach** Inorganic Materials Research Division, Lawrence Radiation Laboratory, and . Departments of Chemistry and Chemical Engineering University of California, Berkeley r January 1968 '" :", Abstract '. Recent proton magnetic measurements in the ternary systems HN0 -, 3 DN03-wa~er and HCI04-DCI04-water partly confirm older data.and furnish . new information of the molecular states of the acids, on hydration and .solvation of the hydrogen ion, and the distribution of H in deuterated acids between the ion and water. The dissociation constants of HN03 and DN0 between and. 25° are derived from the measurements. 3 ° l * 'Present address: National Bureau of Standards, Washington, D. C•• 20234. ** Present address: Institut de Chimie Minerale et Analytique, Universite de Lausanne, Switzerland. ., .. -2- UCRL-18049 . , \ . , .. " ':., " '.1,'....... ". .~ , .'. J 1. Introduction,· ",' ... ~ " ', .. " .,', .... More than fifty years after Arrhenius .. the !nvestigationof the. dissociation of strong electrolytes led to quanttta:t1ve results. The ..... results reported in the. preceding ten papers of ~his se~~esl-10 .. the . , ' . " "11-16 . " " precise work of Young and his coworkers .. and results of later ',,:. ", . (l) O. Redlich and J. Bigeleisen.. J. Amer. Chem. Soc. 22., 1883 (1943). (2) ". o •. Redlich.. E. K. Holt and J. Bigeleisen.. J. Amer. Chem. Soc. 66 .. 13 (1944). (3) G. C. Hood .. o. Redlich and C. A. Reilly.. J. Chem. Phys. 22 .. 2067 (1954).· (4 ) G. C. Hood .. O. Redlich and C. A. Reilly.. J. Chem. Ph~s. 23, 22~9 (1955). (5) "G. C. Hood and C. A. Reilly, J. Chem. Phys. gr... 1126 (1957). (6) G. C. Hood and C. A. Reilly.. J. Chem. Phys. ~ 329 (1958 ) • (7) . G. C. Hood .. A.C. Jones and C. ~. Reilly.. J. Phys. Chem~ 63 .. 101 (1959). (8) G. C. Hood and A. C. Reilly.. J. Chem., Phys. ]g.. 127 (1960). (9) A. Merbach .. J~ Chem. Phys. 46, 3450 (1967). (10) R. W. Duerst .. J. Chern. Phys ... to be published. (ll) T. F. Young .. Record of quem. Progress .. 12, 81 (195l). I I i (12) A. A. Krawetz .. TheSiS, University of Chicago (1955). ',,/ -' , (13) T. F. Young and L. A. Blatz .. Chem.· Revs. '44 .. 93 (1949). (14) T. F. Young, L. F. Maranville and H. M. Smith, in "The Structure of Electrolytic Solutions", W. J. Hamer, Ed. (John Wiley & Sons .. Inc ... " New York, 1959) p.35. (15) D. "E. Irish, B. Mccarroll and T. F. Young .. J. Chem. Phys. 12, 3436 (1963). , (16) E. L. Gasner, Thesis .. University of Chicago (1965). t:· , ,,-3':' .UCRL-l8049 l7 24 . authors - have ~lShed definite information of the mOlecuiar state J • • , of strong acids. ',', In,the present discussion preViohs results on nitric acid and per- chloric acid are interpreted and revised. For some time it had been clear that only measurements extended over the whole concentration range , . '. "1~4 8-10 up to the anhydrous acids' could furnish a satisfactory basis Of, interpretati'on. The extension to DN03 and DC10 was desirable because 4 the great influence of deuteri~~ substituion on proton magnetic reso- 25 26 - , . nance ' promised new information on the molecular state. , . 9 10 ' Two recent papers' reported proton magnetic resonance shifts, obtained within a few ppb for about 80 solutions of each of the two acids between 0 and 65°C., These data lead to definite conclusions concerning ,; , t " ' .' --~' (17) P. M. Vollmar, J,. Chem.Phys. 39, 2236 (1963). (18) R. E. Hester and R. A. Plane, Inorg. Chem. 1, 769 (1964). (19) K. Heinziger and R. E. Weston, Jr., J. Chem. Phys. 42, 272 (1965). (20) A. K. COvington, M. J. Tait and W. F. 'K. Wynne-Jones, Proc. Roy., Soc.' ! 286, 235 (1965). (21) Akitt, COvington,. Freeman and Lilley, Chem. Communications, No.15, Com. 398 (11 August,·1965). (22) D. E. Irish and G. E. Walrafen, J. Chem. Phys. 46, 378 (1967). , - (23) J. T • Miller and D. E. Irish, Can • .J. Chem. ~, 147 (1967). • (24) A. K. Covington and T. H. Lilley, Trans. Faraday Soc. §l, 1749 (l96l). _.J (25) A. J. Kresge and A. L. Allred, J. Am. Chem. Soc. §2, 1541 (1963). (26) V. Gold, Proc. Chem. Soc. !2§l, 141. ·-4:.. ", . , , " , . ~ . '" the ,states of tl1e acids:Ln the whole ternary fields. ,Yet tlleinforma- . : " . " - . tion does not appear to be fully exhausted and further conclusions beyond the present discussion may ,be. expected. " ' 2. 'Deuterium Substitution' Various peculiar features of the influence of deuterium substitu- • ,,' ' , ,tI tion have· been discovered during the examination of the data. ,'., . '. 21. High· Concentrations , ..... In some concentration ranges the influence of deuterium substi- " , , tutionis very strong, in others it is negligible. The difference is ""', characteristic~ , . 10 The shifts of anhydrous, HCl04 and DCl04 are equal within the narrow limits of experimental error. What is called "shift of DCl04" here " is actually the shift of the proton in DCl04 conta.ining 0.210 Hql04. ,The independence of the shift of the D-fraction means that the replacement of HCl04 by DCl04 in the environment' of the proton does not affect the shift ,of proton. The result is good evidence for the monomeric state of the anhy- .- drous acid since a replaceIl!-ent of H-bonds. by D-bonds would be expected to change the internal field at least by a small amount. The nuclear magnetic resonance (NMR)of nitric acid ,depends strictly, linearly on Gutowsky's variable27 p = 3x/(2-~) (2.1) " in the mole, fraction range 0.6 < x < 0.95. The linear coefficient A2 (27) H. S.Gutowsky and A. Saika, J. Chem.Phys. 21, 1688 (1953). ".1 ., ,.; -5- 'I ',' . ' .. ' .:" .~ .' 'is represen~e~9 as a function of the isotopic ato~' fraction ,'f .. ~~ j . r, = D/(H+D) . -," '~ ,I and the temperature t by " 2 )1 A = 1.428 - 0.016r +, ,(0.087 t 0.047r)·::J..O- t '.1 • 2 '. l The 1:l:nea~1ty was interpreted as anind1cation of'the stoichiometric":', ~ '/ \J rl . completeness of the reaction ~1 'I -.J ,I (2.4) 1 ,t, il ,{ !L The dependence of ~ on r is zero at 38°c and hardly more than the ~,, ,l errors of observation and smoothing at other temperatures. ... : " , .!, : ." ·j The ~ependence on r of the specific shifts s2 of H3N04 and s3 of t• ~ _(HN0 )2" as given later in e~uations (3.4) and (3.5), is slightly higher 1 3 j but still rather small. ( , These results suggest some general conclusions: The proton-deuterium Ij i 1 distribution between uncharged molecules is nearly uniform. The' inter- ·f ! action of non-bonded molecul~8 is not appreciably affected by the iso­ I I topic substitution. I The results are in accord with the molecular interpretation given. ! L " 22. HYdration and Dissociation Deuterium substitution greatly increases the shift for the .' lower range ex < 0.5) of both acids and .also for the upper range of per- l , " chloric acid. These are. the solutions containing hydrogen ion in large 25 26 concentrations. Earlier authors ' have already concluded from the observed ratio of the limiting slopes sll of DC104' and 810 of HC104 that the proton ,has a strong preference for the ion over water. This conclusion, , '. ", ·.·.-6- . " .' • ,I ~ •• . , extensive experimental data, of high precision. A survey 'of the data now available for the lower range shows several peculiar features of the shifts. The ratios/pis shown as a function '(.. of the mole fraction x of.the acid in Figures 1-3 for nitric acid and in. , Figures 10-12 for perchloric acid. The curves of sip show an approach to a horizontal limiting tangent at x=o fOr'HN0 at OoC (Figure 1), 3 . , " , hardly at 25°C (FigUre 2) and not at all at 65° (Figure 3).
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