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Chem. Thermodynamics 1987, 19, 417-431

The standard enthalpies of ionization of sulfurous acid and the standard enthalpies of solution of sodium sulfite and sodium metabisulfite in water at 298.15 K

CECIL E. VANDERZEE” and LEO A. NOLL Department of Chemistry, University of Nebraska, Lincoln, Nebraska 68588-0304, U.S.A. (Received II June 1986; in jinal form 8 September 1986) Standard enthalpies of ionization of sulfurous acid and the standard enihalpies of solution of Na,SO,(s) and Na,S,O,(s) in water at 298.15 K were measured by solution-reaction calorimetry. All operations were carried out under N, with particular care to exclude 0, from the reaction system. Steps in the corrections to the standard states are outlined in detail. The results (mean + uncertainty interval) are: AiOnHG(H,SO,, aq) = -(17.82*0.18) kJ ‘mol-‘; Ai,,H;(HSO;, aq) = -(3.67*0.06) kJ,mol-r; A,,Hk(Na,SO,, s) = -(13.261!10.06) kJ,mol-*; and A,,,Hi(Na,S,O,, s) = (21.34kO.07) kJ.mol-’ for the process: Na,S,O,(s)+ mH,O(I) = ZNaHSO,(aq). For the equilibrium: 2HSO; (aq) = H,O(l)+S,O:-(aq), we selected K” = 0.032 and A,HG = -4.2 kJ mol-’ from the literature.

1. Introduction

The primary objectives of this work were to determine the standard enthalpies of solution for sodium sulfite and sodium metabisulfite, Na&O,(s), and also the standard enthalpies of ionization for sulfurous acid, H,SO,(aq), where H,SO,(aq) by convention represents the equilibrium mixture {xH,SO, +(1 -x)SO,} in solution, even though x is small (0.03 to 0.07). (1*2) Previous measurements(3) of the relative apparent molar enthalpy L, for Na,SO,(aq), together with estimates of L, for NaHSO,(aq), provided values for making corrections to the standard states, The standard enthalpy of solution of Na,S,O,(s) was referred to the process: Na,S,O,(s) + H,O(l) = 2NaHSO,(aq). The metabisulfite ion, S,O:-, exists in aqueous solution molalities of the salt as a result of the equilibrium: 2HSO;(aq) = S,O:-(aq)+H,O(l). at moderate (1) to high (2)

Connick, Tam, and von Deustert4’ recently reported results of a careful study of reaction (2) by Raman and ultraviolet spectrophotometry. They measured the

’ To whom inquiries should be addressed. 0021-9614/87/040417+ 15 %02.00/O !c; 1987 Academic Press Inc. (London) Limited

02 mol. solution.(s). Solutions of HCl were standardized against an NaOH solution referred to primary standard potassium hydrogen phthalate..O in the Na. from which they obtained A.S..‘4’ also made measurements at three other temperatures. and 190. when heated. Corrections for the small amounts of sulfate present in the sulfites are not negligible but are easy to make.S. 126.105 g.(s). In another procedure. lot YRP. with standard Na.O. atmosphere for handling of chemicals and solutions.H.3 kJ mol-’ at lower ionic strengths. Na. and Na.SO. from cylinders was used to provide an N.S.(aq) is relatively easy and introduces only small correction terms.O to collect the entrained H. Dry N. 2. the corrections for effects of S. (aq) near 0.1 mass per cent of H.O.15 K. Molar masses of KIO. and Na. kg.S. Mass-buret techniques were used for all analyses.‘.02) mass per cent of H. Throughout these measurements. Mallinckrodt AR. was precipitated by addition of BaCl. E. mol. mol. Doubly distilled water was collected and stored under N.O. Connick et a1. All solutions were prepared and analyzed on a mass basis. as primary standard.t3’ The solids were assayed for sulfate by gravimetric procedures. + KI) and Na.6 kJ .. the solutions were boiled to expel SO.SO.‘.S.418 C.(s) samples and (0.O. This procedure indicated (0.(2) = -4. is the activity coefficient function for reaction (2) at several ionic strengths.O:-(aq). as for the dilution studies on Na.(s) samples..005. Baker and Adamson.SO. into an excess of air-free (I2 + KI) solution and back-titrating the excess I. was passed through the tubes and then through an absorber containing CaSO.O in the Na. and Wilf’a’ confirmed Gelding’s”’ measurements and reported results leading to A. = -3. and starch indicator. were taken to be 214. The solids were assayed for sulfite content by transferring a measured mass of sample under N. Their results are reported graphically but two numerical values are cited at 298.O. Samples of Na.(s) .042.are practically negligible (Z 4 J.SO. The Na. mol-I.. and also for protection of calorimeter contents. and BaSO.12+0.Og. were used as received.02) mass per cent of H. At higher molalities the corrections can be calculated with sufficient accuracy. all preparative and calorimetric operations were carried out under an atmosphere of nitrogen to avoid as far as possible the effects of oxidation of sulfite by oxygen during the calorimetric measurements. Experimental MATERIALS AND ANALYSES High-purity N.SO..SO. VANDERZEE AND L. Hayon. +H.09+0.‘). Control of the hydrolysis of SO:-(aq) and ionization of HSO. had small changes in mass corresponding to about 0. were intercompared and referred to KIO.H.‘3’ Samples (about 1 g) were dissolved on hot air-free HCl. NOLL equilibrium quotient Qn = Kb/&. samples of the solids were placed in tubes which could be heated in an oven.(aq).O. The results of previous investigations’*-” are less accurate but are in satisfactory agreement when recalculated with the more recent valuec4) of the molar absorptivity of S..O. A. At molalities of HSO. Na. respectively. and will be described in a later section. Treinin. where r. Solutions of (I.

O.55kO..: (98.1.: (O. and (0. operating patterns were normal.15 K.25 kO.+0.SO.2. In most runs.09+0.12+0.SO. and (0.63 kO. Calorimetric samples were weighed into 10 cm3 glass ampoules under N. and the ampoules were sealed with a Teflon plug and wax seal.08) mass per cent. Because of possible perturbing effects from oxidation of sulfite by traces of oxygen during the runs. Calorimeter temperatures were measured to + 1 x 10e5 K with a Hewlett-Packard M40-2801A quartz thermometer operated in the 100 s range with minimum time between readings.) mass per cent of Na..(s) samples assayed (66.05) mass per cent of Na.SO.2.O.ENTHALPIES OF SULFITES AND SULFUROUS ACID 419 samples assayed (99. The Na.2.02) mass per cent of H. and were referred to this reference temperature (0.) by the equation:“3’14) (3) in which ci and sf are the electrical energy equivalents determined for the initial and final states of the process. (0.02) mass per cent of Na. with minimal exposure to air.02) mass per cent of H. 0.02) mass per cent. are the calorimeter temperatures at the beginning and end of the main period. CALORIMETRIC EQUIPMENT AND PROCEDURES The solution calorimeter has been described previously!‘-” and its performance has been monitored for several years. Reaction STANDARD ENTHALPY OF SOLUTION A. s).O: (0. The ampoules were mounted in the sample holder and then the empty calorimeter vessel was attached. The small amount n3 of NaOH was added to suppress hydrolysis of SO:-(aq): a .lOf0.. Any evaporation effect from this gas flow makes an essentially constant contribution to the temperature-drift rates and does not complicate evaluation of the last term in equation (3). and A@.SO. and then the calorimetric solution was transferred into the vessel from a 1.12 kO. temperature-drift patterns and thermal moduli were monitored closely for evidence of such perturbations and needed corrections. and 0. 3.S. (12) The jacket (thermostat) temperature was controlled to 13 x 10e4 K. The empty assembly was purged with N.. and H. is the temperature-change correction for stirring and heat exchange. (1. patterns and results OF SODIUM SULFITE Chart 1 represents the network of processes leading to As0rH~(Na2S03. and were recorded by a digital printer.55 kO.) mass per cent.02) mass per cent.O.3 cm3.2 to 0.SO. following procedures outlined in reference 14.06 dm3 delivery bulb which could be weighed before and after delivery.O. (0. for several minutes.H = E~(O~-O~)+E~(O~-O~)+(E)AO. s-‘) was maintained into the calorimeter through a chimney vent during delivery of the calorimetric solution and during the run.08) mass per cent of SOZ. All of the results refer to the isothermal calorimetric process at 298. Na$.+0. A slow stream of N. Corrected temperature changes were evaluated by standard procedures” 3*14) and programs adapted for quartz thermometry. These results were interpreted as Na. Na.: (1.

(4) In applying equation (4).SO. C. to be equal to L.SO.Hm(Na2S0..” 3. Aso.)Na.Hi.(s) + coH. AH. kg . were taken for the components at the ionic strength of the mixture.SO. +n.n2 As.‘16’ Table 1 represents the experimental results for chart 1 and the standard process: Na.SO. (n2 + n.(Na. the dilution corrections involve only the sums (n4 + n5) and (nl + n. with sufficient accuracy. A. mol.(Na.SO.)Li(Na.)Na. (5) The uncertainty interval includes estimates of contributions from systematic errors in the terms in equations (3) and (4).SO. respectively. VANDERZEE AND L.SO. The ratio n5/n4 may be larger than n2/n1 due to oxidation of sulfite by residual oxygen in the solution.06) kJ.43 kJ. s) n. Na.Na. The contributions from terms in equation (3) .(s).+n. for Na. so the effects of the approximation are practically nullified in the calculation of Aso. From chart 1.).O(l) = Na. Aso. .). + n.005 mol. and the isothermal calorimetric process is identified with A.0 I n3 NaOH (nl + n.SO. E. The superscripts i and f refer to the initial and final states. For Na. with L+(Na. A small amount n4 of Na2S03 was needed to scavenge residual traces of 0.)Na.) was also used in the evaluations’3’ of L+(Na. The solid sample contained a small fraction n2/n1 of Na$O. NOLL CHART 1 n.. the values of L.(15) Values of L.SO.SO. . -(nl s) = Ar H + (n.SO. for Na..(n. coH.Hi(Na.Hi(Na$O....) +n.)+ . but since we can take L.2640... n.) = L.’ is adequate.NaOH ‘(n.420 n..H.SO. The approximation that L+(Na.’ .).SO. +n.{L$(NaOH)-L!&NaOH)}.SO.mol-‘.) = L. coH. s) = -(13.(s) which was assumed to be present as a separate phase in the solid mixture.O.O molality of 0.SO.+n.(s) n.SO. which are not changed by the reaction with residual O2 in the solution. and the enthalpy of mixing or unmixing at constant ionic strength was taken to be zero.SO.SO. from the solvent before dissolution occurs.(NaOH) and other uniunivalent electrolytes used in this work were taken from Parker’s compilation.Hm = 2. A. (r3) This rule was followed in all of the calculations in this paper.)Na.)Li(Na.S’O.

506.mol-’ for the mean+2c. The major contribution from equation (4) is that from L+(Na. and is most likely so because of residual traces of O2 in the calorimetric solvent. 6 x IO-’ K. Mean k 2~7.Hi(Na. This would indicate a residual oxygen content of about 1.066187 0. kg-’ in the diluent solution. Sulfate content is obtainable from the ratios n&r.005834 0.‘14) whereas for the series in table 1. Symbols correspond to chart 1 and equation (4).005834 AH -L J -539.). In the buffered calorimetric solutions. mol-‘.5. 298. -476.0669 .54&0.005834 0.082461 0.065533 mol 0.13.H: kJ.0645 1. from (0. 4 n4 n3 AM E kg mol 0..H~(Na. 3 x lo-’ K.005834 1. the ratio n(H.-(aq) + H+(aq) = HSO.24 . -479. there were some runs with strong linear perturbations of drift rates.).9.26 + 0.20 -13. THE STANDARD ENTHALPY OF IONIZATION OF HSO. - 13.0669 1.005834 0..005834 0. uncertainty interval: kO.039832 0. kg-’ and the final ratio (nl +n3)/(n2 +n.)/n(HSO.0669 1. the initial and final mixtures can be regarded as independent solutions of each component.) is less than 0.42 ” 13.(aq) The quantity AionHi(HSO.005834 0.‘.SO. representing the molar mass of H. estimated at 40 J.15 K).SO.. -535. -512.(13.2...SO.. For the series with n4 = 0.) z 2. A@.5.0645 1St645 1.0655 I .3.041954 0.0655 1.039760 0. 0.045435 0.10783 0 0.042292 mol 0.. As in chart 1.041954 0.005834 0. s) = -(13.06 kJ molt ’ are estimated to be: from E. From a series of 8 runs with we obtained made n4 = 0.. Oxidation of sulfite to sulfate by oxygen releases about 566 kJ * mol.13..mol-’ .O.33 0.7. -490. with M. -480.0001 and there is no significant .040506 0.5 mol.. The procedures outlined in reference 14 were developed partially in connection with these runs. for which the appropriate flow-chart is represented by chart 2.02 per cent or 1 J.044733 0. for 8 runs: . s.7. each in the hypothetical-ideal standard state without ionization or hydrolysis of the anions. K.0655 1. z 0.005834 0.13.26 13.3.9 x lo.23 13.020800 0. The excess enthalpy amounts to 11 J * kg-’ of solution..039761 0. Experimental results leading to A~.. = n&t. made with more thorough exclusion of 0. ho.‘. -487.’ of 0.040239 0.0056. A.26 . +SO.O. protonation reaction: aq) is obtained from a calorimetric study of the (6) SO. This result was more negative than the result from the series in table 1.ENTHALPIES OF SULFITES AND SULFUROUS ACID 421 TABLE 1.(aq). drift-rate perturbations were small.04) kJ mol .07) kJ.3.10595 0. = 0. .020752 0.25 a Not included in the mean.02 mol.34 -13. made earlier than the series in table 1.SO. with initial molalities m2 z 2m.

‘~’ We estimated L.) = (1 -a)L.O.) by ..SO. HCI I I AH. represented by L. Then from chart 2.(Na.)} + n2{ L$(Na.SO.+(NaHC03) at these ionic strengths.H +n.0 4 n.-n.‘*) The corrected results from the two sources were in good agreement. mol. HCI ceH. n. VANDERZEE CHART n.Hk(2).(n.Na. aq) = A..)) n3{L. A.SO.‘n. I I .S.(NaSO. -n.(Na.)Na. measured by Connick et ~1.’ was found by applying estimated dilution corrections to the values of ArH.C03).Na..~ mH.) = L.OzP.‘n.)Na.) .NaHSO.)-L$‘(NaHSO.) = L@(Na.S.SO.&Na.) is only slightly larger than L+.n.~(A+B)H. zH.2 kJ . (I’) based on the observation that L. ‘(NaHSO.Ai. The value of A..{Lk(HCl)-Li(NaCl)+ L$(Na.)+(a/2){L+(Na.Hk(HSO. n.)NaHS03~n.SO. Following procedures outlined elsewhere. is practically negligible because n.‘3* “I which strongly implies a close similarity in L.NaHSO.)NaHSO.SO. We estimated L.&NaHSO.NaCI.H~(2)}. +n.) changes by only a small amount at the ionic strengths used in this work. H:(2) = .SO. in the mixture affects Ai.NaCI.O n.L$ ‘(NaHSO)) +n.) .(NaHSO.SO.Hi(HSO. and NaHCO.SO.) .SO.SO.045 kg.Na.EH..‘14* “) we obtain L.(NaHSO.SO. to Lz arises from A. converted to S... (7) Again we took L.4. There are few similar electrolytes to use as analogs.SO. (8) in which CI is the fraction of HSO. In equation (7) the total correction for Na.L$(Na. is small and L+(Na.(n.SO. E.Na. The influence of Na$.)}. (3) The dilution term involving Na. from the equilibrium.‘~’ and by Hayon et al.) by analogy. mol-’ from the results of Connick et ~1.or SO:-. reaction (2) requires evaluation of the relative apparent molar enthalpy for the equilibrium state. and is evaluated from K(2) = Qu = 0.-n.S20.‘(n.). The primary term in the correction from L. for NaHSO.O hydrolysis of SO: .0 n.SO.O ArH i.SO.Na.n. NOLL n.SO& to be consistent with approximations made in evaluating L+(Na...L:(Na.) = L.(n.O AND 2 L.{Lk(Na. +n.422 C.O.S0./n.Na.SO.(Na.)+A.O.

’ 6 J.01055 0. The uncertainty in the estimate of L.) kJ*mol-‘.mol-‘.0592 1.0578 1. n.01021 0.021214 0.A.O(l) and HSO.cQ971 mol 0.98 14.mol-’ -3..SO. which was omitted from the mean. and the amount remaining in the final state is (n3 .H(lO)-n.010948 0.2n. Errors in n2 and n3 arising from uncertainties in the assays of the solid samples have negligible influence on the corrections.05 15.H~(HSO.00023 1 0. n2 n.Na. AJ J 16.(s) + 2NaOH(aq) = 2Na. Table 2 contains the experimental results leading to: Aio. 298.00948 0.021219 0.(s).SO.010801 0. aq) = ..S.(aq) to yield reaction (1).010532 0.63 12.Na. with M..010076 0..000233 0.OCKI235 0.SO. s) (11) +(n.(‘4) and presented no special problems in evaluating the heatexchange corrections.+n&.010063 0.009836 0.O(l). 298.SO.06. (2) a slight excess of NaOH is used.010711 0. Experimental results leading to AiO&(HSO. (9) for the mean and uncertainty interval. Then n.07 kg 0.01065 0.S.45 16.021526 0. mol 0.+n.010686 0.)-(n.) is estimated as +30 J. AHL(10) = A. * n. Na.15 K).(aq) + H..Na. representing the molar mass of H.726 -3.010525 0.01041 0.0596 1. Mean + 20.74 13.ENTHALPIES OF SULFITES AND SULFUROUS ACID 423 TABLE 2.616 1 ’ Not included in the mean.010593 0.A.0583 1.f0.O AM.010564 0.00970 o.Lk(NaOH) -(2n..66. Run 5. mol. .+n. HL(HSO. residual oxygen in the ampoule solution should have produced an error of 10 J.020911 0.O.48 16.000231 0.15 K) = -(3.0582 1.-2n.). aq. Most of the runs had temperature-drift patterns close to normal..736 -3.+n.)Li(NaOH). kJ. with each compound treated as a separate phase..SO.H:WSO.610 -3.000235 kg 1. with only small linear perturbations in the after-periods for the reaction.669 + 044) kJ mol. THE STANDARD ENTHALPY OF SOLUTION OF SODIUM METABISULFITE One reaction of interest is (10) which can be combined with the ionization of H. Under the handling procedures followed in this work.+n.Hk(Na.000273 O..517" -3..O. .“4’ The uncertainty interval was evaluated as for reaction (5).(NaHSO. for 6 runs: A. Symbols correspond to chart 2 and equation (7).011053 0. s)-n.mol-‘. The last term in equation (7) is the largest correction and is the main source of error in the corrections to the standard state..)LfQ(Na.SO.667 -3.(3. was suspected of having a much larger amount of oxygen in solution.010727 nA BM.660 -3.Hz(Na.021125 0. The flow-chart for reaction (10) differs only slightly from chart 1: (1) the solid sample is n..000229 0.021515 mol 0.0596 A.SO.031509 0.’ or less in Aion HL.)+n..010475 0.(Na.0596 1.

-97.‘).2502.O(l)).3 -2481..061303 0. Errors in the assay of the solid sample of Na. and n6.A. Chart 3 shows the set of processes leading to A.(HSO.Li(Na.a(H2S03) -Li(H.63.025939 0. VANDERZEE AND L.2 .8 interval: k0..(Na.A.061465 = -97. -97.O. A. but the HCl solution was deoxygenated by sparging with high-purity N.Li(NaC1) + Li(HCl)) + n. kg 1.2604. with AM.060606 0. -97. NOLL TABLE 3. To simplify the corrections.O in the calorimeter initially.L+(HCl) .A. kg. uncertainty W J -2485. Experimental results leading to A&(10) for Na.021 I.63.Hz(HSO. = 0.moll’ separately at essentially the same ionic strengths (I z 0.).O.61 kJ.S.020259 0.( 10) __---kJ.(2n.2630.) + X{AionH.)-n. -97.(l) is given by: n.(aq). Consideration of estimated contributions leads to 0.) is taken equal to L. -97.72.6 .) ..) = L+(NaHCO.Yj.1121 1.1109 1.61 fO.50. the standard enthalpy change A.n. n. -97.027391 0..062433 0.)+n. Thus.(s) in a dilute acid solution to control hydrolysis of HSO. In blank calorimetric experiments. .H~(Na.S. .061218 0.424 C.mol-‘.mol-’ -97.Hi(lO).1133 I. and was carefully protected from 0.Li(NaHS0.0973 1.1134 1.) as an adequate approximation.S04) . Quantities n2.026583 0.020748 0. in which a small amount of sodium solution was added to the acid solution.(aq). and partially compensatory with respect to A.mol- AM.ff.: n5/n4 = 0. + n&2 ‘(NaHSO.Li(NaCl) -(n3 -n. and are largely compensatory insofar as the corrections are concerned.SO.SO. during all operations..0015.l for the uncertainty interval for AHk(10).HL(l) = ArH-n.57.S.07 kJ. no sulfite was added to the calorimetric solution. From chart 3. being the mass of H..(s)+ZNaOH(aq) ZNa.)L~(HCl)+x{L~‘(NaHSO.0 . as in equation (4). mol-1.020720 0.Jnl = 0.12 mol.025901 0.09 to 4. affect mainly the terms in n. and usually results in formation of small amounts of H.) .(NaHSO.Ai.SO. The first two correction terms in equation (11) are relatively small.1137 1. The term is that involving ionization of H.mol-‘.SO. mol.(aq)+H.020751 0.) in the mixtures. for which (AionH~(H2S03)-Li(HzS03)} = -(17821 f 180) J.Hg(l). kJ.) . the thermal response indicated that the 0.026087 Mean: AWlO) n3 mol 0. L+(Na.SO. A.SO. and. Symbols correspond to equation (1 I).SO.lO) kJ.5 . The corrections become more complex than for dissolution in NaOH(aq).2548.059077 0.O. E.020737 2a. = 0. but enough information is available for them to be made.1148 1.H. ngr and n6 can be calculated from the ratios: nz/n. We can take largest correction the combination was measured 0.020805 0.)-Li(NaC1) + Li(HCl)} + z{ Li(Na.. concentration was at acceptably low limits.027146 0. % mol 0.nl mol 0. A direct approach to reaction (1) requires the dissolution of the Na.020783 0.n.10 kJ.68. (12) The experimental results for this route are given in table L+.50.10 A.027655 0.H~(Na.059229 0. Table 3 presents the experimental results.SO& +zAionH.0056.Hg(lO) = -(97.2 -2656.SO.

SO.050330 0.OC0085 i&i 0.6 1509.O. Symbols correspond to equation (12) and chart 3.S.O n.)m”] = KY/T.NaHSO. with M.(H.+(n.O 1 ((2n.HCI)}~coH. Calculation of the composition variables x and y requires values of the ionization constants KT for H.O Equation (12) then yields a value of A.055271 mol 0..+zNaHSO.016) uncertainty interval: 170 J.001063 0.313 21.O j(2n.001074 0.)H.O(t) = 2NaHSO.001224 0. +(n:-z)Na..SO.1719 I. = Kz/T. -~--.HCI.001303 0.I641 1.SO. The uncertainty of _+180 J. 0.3 1271.333 21.(A+n.366 21.+n.057946 0. and r. being the molar mass of Hz0 nI I.mol-’ .mH.Hk(t) which is independent of the value assigned to L.SO. mH.000078 o. +xHzSO..5 kJ.S.(s) n._ --_.ooucl91 O.oooQ95 O..-x-z)HCI}.+zNaHSO.-n.SO.011343 0..HCI. mol-’ to the uncertainty in AH:(l).050869 0.+n.AH.-0.NazSO.-x)NaHSO.: m(H+)m(HSO~)/{m(H2S0.mol21.OOtKt89 o.(s)+H.6 1368.1346 1.mol-‘. (13) (14) TABLE 4.334 ’ Mean _i 2u.Na..Na.011275 0.362 21.011646 0.-.(aq) and Kz for HSO.(aq).011307 0.O.‘n.+x+z)NaCl +(n.n. mol-’ contributes +30 J.4 1447.011569 0.)m”) m(H+)m(SO~-)/(m(HSO.SO.011622 mol kg --.1695 - J 1254. Experimental results leading to Ar..).342+0.-n..-x)NaHSO..Hm(l) for reaction (1): Na.+xH.+(n.001167 kJ.SO.(aq).1.1378 1.+x+z)NaCI +(n. +n.344 21.(l) .-x-z)HCI}.: (21.061675 0.1414 1.i % n2 n3 AM _4H &H. -z)Na. +n. since x/n1 x l/6.Na.000078 0. together with the corresponding activity-coeffocient functions r.8 1432.058892 0.O I 1 j2n.+(nzNa.001244 0.ENTHALPIES OF SULFITES AND SULFUROUS CHART 3 ACID 425 n..SO.+(n.

The uncertainty interval given in table 4 includes these among other estimated terms. STANDARD ENTHALPY OF IONIZATION OF H.‘j2 by a graph. based on Huss and Eckert’s work should be valid for our mixtures and should provide a quite reliable basis for calculation of X.(aq) Measurement of Ai. and m“ = 1 mol.‘20’ and Devese and Rumpf. .’ is strongly supported by those of Britton and Robinson.0002) at 298. values of KY/T.). z/x z 0. the amount of substance reacting according to equation (16) must be calculated in terms of the ionization constant KY and its related activity-coefficient function Z-i.(aq) and HSO.15 K. with the usual approximation that y. with c( based on K. Thus.048 kg.(aq) = H+(aq) + SOi-( (17) which also contributes to the calorimetric response. from 0.SO. A..0265 to 0.(aq) is a relatively strong acid (KT = 0.07) J*moll’.0139 & 0. ranged from 0. kg-‘. For HSO. aq) is complicated because H. A 10 per cent error in z would contribute an error of about 4 J.(‘s’ so its solutions are a mixture of H.0139 when recalculated with the common values of r.(l) = (21. with similar calculations for the sulfate impurity and the process: HSO. mol-‘.H.SO. The error in x should be no more than 1 per cent and contribute no more than 30 J.0139). A.09.H.(l).(aq) = H+(aq) + HSO.(aq). The calculation of solution composition before and after the calorimetric process is the same as for the final mixture in chart 3. mol-’ to the error in A. VANDERZEE AND L. from Huss and Eckert. Huss and Eckert”” recently reported KY = (0. Our evaluations could be represented by equation (15) with B = 1. Huss and Eckert’s results lead directly to r. The other major contributor is L?‘(NaHSO. together with the related activity-coefficient function f. but do not present an unambiguous combination of the parameters in the equation: In y+ = .342kO. (21) Other values’22*23’ fall into close agreement with KY = 0. so the estimation of r. = 1 for the neutral species in equation (13). (13 to correspond to their figure 3.(aq).H~(H. E. At equilibrium in these mixtures. In the above calculations.A(I/m”)“‘/{ 1 + B(I/m”)“2} + C(Z/mO).01.0283.0221 to 0.S03. evaluated by equation (8).643 and C = 0. = Z-f as an estimate for r.0228 and K”/T. mol-’ at these ionic strengths. mall’.“” At the low ionic strengths used in our work.0105 based on CODATA selections’24’ and used r. the amount of SOiand OH-(aq) are negligible. = y:/yo.426 C.. For H. equation (13). For our mixtures. NOLL In our mixtures.SO. (16) or the reverse (protonation) reaction. K”/T.SO.SO. Consequently we evaluated I’* directly from the measured results in their table II. introduces little error. with the Debye-Hiickel parameter A = 1.O:ranged from 29 to 36 J. Then for calorimetric studies of the reaction: H. Their value of K. = 0. Huss and Eckert present their results for the activity coefficients I’* = r.“‘) Ellis and Anderson. solutions.176.. Here the correction for S.(aq) we used the value K” = 0.

+z’NaHSO. the same symbolism is used.-n. /. These procedures reduce the experimental time and avoid transfer of oxygen-sensitive solutions.-x-z)HCl}.+x+z)NaCl+(n.O 1 {tno -. helps to increase the amount of added H+(aq) consumed in the protonation. Electrical calibrations were made before and after each reaction step. +(n.SO. Calculation of ..” ‘) The first ampoule was filled with the solid sodium metabisulfite and the second with 2.-)‘)NaHSO. = Zn..+xH. so KY/T.O ~ .+(n. except that n.‘)Na.x)~aHS0. A substantial excess of NaHSO. The relative apparent molar enthalpies f. To maintain the close relations between charts 3 and 4 and tables 4 and 5.+(n.+n.HCI~BH20 A? 7 ((n. The ionic strength changes by only a small amount in the calorimetric process.coH.xH.+(n.O [(n.Na.)HCI+n.+.-‘)NaCI +(n.-n./n.)HCl+n. differ by only small amounts between initial and final states. Collection and .-y-z’)HCI}.(aq).+(n.Na.SO.SO.NaHSO.+ change by only a small amount as well.-n. +xH.-~‘)Na.NaHSO. -z)Na$O. kg.-x)NaHSO.--.SO.v and Z’ followed the same procedures as for x and z.+n.O I {n.+(n.+n.SO.+yH.SO. and Ki/T.+n.HCI .+(n.-’NaHSO.O 1 ((n.667 mol.NaClj~H.O n.-n.O Chart 4 outlines the network of correction steps for a calorimetric study of the protonation of HSO.SO.ENTHALPIES OF SULFITES AND SULFUROUS ACID 427 CHART 4 jn. the overall value of AH” for chart 4 is zero. A very efficient procedure is to use the final calorimetric solution from chart 3 as the initial calorimetric mixture for chart 4.-y)NaHSO. 1 +zNaHSO.SO. This was done by using two ampoules in the multiple ampoule holder. +n.-z)Na. so the dilution corrections have several small difference terms. +(n. As written.SO.+y+i’)NaCl +(n.+(n.-x-z)HCI}~AH.+.(A+B)H.+n.NaCl} ccH. +(n..mH.+yH.x+z)NaCl+(n.+y+.’ HCI solution. Computational time is reduced since the last two steps in chart 3 are the reverse of initial steps in chart 4.-n.-y-z’)HCI.-n.+zNaHSO.

mol-‘.)} + n.01032 0. are closely correlated in their evaluation.).1641 1. with M.(NaHSO. mol. L. many may choose to set L+(H.): Mean f 2a.011343 kg 1.(H.12345 0. E..)} + z(L+(HCl) -L$NaCl) + L$Na.) + La(HCl) .) kJ.) becomes available. f 180 J .‘.)} +n. since Huss and Eckert’s values”*’ of KY and I-.00965 0.SO. To a first approximation. since it will be quite a small term.)).82+0.)-LO(H~SO~)) = -A.011622 1.JH.{L.) = 0.025711 0.O0077n.10182 0. .L$(NaCl)} + x{L. Our first approach is to isolate and evaluate the combination: (Aion Hi(H.(H.001063 0.11598 0.L$(NaHSO. At our ionic strengths.). The precision of the resultant values of is good.(HCl)-L$4(HC1)] + n.027514 0. n2 n3 AM.11787 mol 0. with the difference term (Li -Lb) z (0 f 10) J.mol-‘. with the approximation that L.mol-’ -17.{Li(NaCl) .SO.8.00989 A.: -(17. ‘(NaHSO. being the molar mass of H. and with n6 = O.001074 0.7.428 rearrangement C.&--L+)(H.011646 0. estimated at (285+30) J.) + n.026381 (A. but are probably small.1346 mol 0.901 -17.6& 244.18) kJ. L.) .00964 0.011307 0.82. ‘(NaHSO. Table 5 contains the experimental results.. mol.20 269.L.SO.r from the uncertainty in L+(NaHSO. A.1414 0. Symbols correspond to chart 4 and equation (17).Li(HC1) + Lt(NaHS0.SO.(H.SO.mol-‘.L.755 1.H-(z’-~)A~.00858 0. VANDERZEE AND L. The error in (y-x) should not exceed 1 per cent.Li(HC1) .CO.001224 0..)}.05.1719 1.760 -17..896 -17. 260.(HCI)L. At some later time.SO.) . 0. NOLL of terms leads to the relation: (~-~){A~~~H~(H~SO.H~(HSO.SO. (19) TABLE 5.011569 0.025726 0.10074 0.(HCl)} +n. when L.L$.) is essentially constant for our range of ionic strengths. mol-’ at these ionic strengths.{L. For comparison.(aq) in the process.L$(NaCl)} + y{ Lt(NaC1) . The next largest estimated error is + 60 J. (18) in which (y-x) is the extent of protonation of HSO. includes these and other smaller estimated errors.) kJ.7. uncertainty interval: . AionHi(H2SOJ) can be obtained from our results.L&H.) = 0.1378 1.001167 0.(Na.) are not available. &. ‘(NaHSO.SO.mol-r. n4 “0 mol 0.) would be about 45 J.Li(Na.)} + z’{Li(NaCl) . With the approximation that L. 270.1695 0.022888 EM I kg 0.H J 270. The estimated uncertainty interval. The sulfate impurity correction is appreciable but leaves no significant error.SO.SO.001244 mol 0. This is then the combination term needed for equation (12) to calculate A.801 -17.SO.{L.. we have AionHz(H2S03. aq) = -(17.(LiNa.SO.) should be close to its maximum. ‘(NaHSO. +0.026175 0.(H. considering the number of corrections {AionH~(H2S03)-L~(H2S03)} which must be made.001303 0.)L+(H. mol-‘.40 276.O.814 -17. Experimental results leading to (A.) ..00981 0.11063 f 180 J. Values of L.) .Hk(l).Kt.011275 0.H:-L&HW.SO.

118 mol. the comparison can be expressed as: AionHz(HSO. The effects of the corrections for the formation of S.O:-(aq). however.O:-(aq) was omitted.1 mol.O) = (55806+40) J. calculations were also made for a curve corresponding to I = 0.kg. aq) = .1 mol. ye = 0.094 to 0. the effects of S. We retained their choice for the ion-size parameter and used guidance from analog curves for similar l-l electrolytes’25’ in selection of the linear term Cl in equation (15). The uncertainty interval for the indirect route takes into account some partial compensation of errors in the ditition corrections and the other correction terms. and Ai.Hk(l) can be calculated indirectly from the combination: {A.Hk(H2S03. Discussion In the evaluation of terms in equations (12) and (18).Hm(HSO. This comparison reveals that A.HL( 1) = 21.055 mol. mol.340+0.. mol’. mol. The uncertainty in the S.Hk(H. but is probably more suitable for a mixture in which the primary cation is Na +(as).’ (direct route). so in calculating dilution corrections on H.. in the calculation of A.SO.829 at These yielded: AionH~(H2SOJ. A value of A. kg-’ for our solutions.Hk(l) = (21.O) . mol. Other sources of error have been discussed with the presentation of results. so it is necessary to adopt a function such as equation (15) for extrapolation to the range 0..O:-(aq) corrections should be no more than 10 J. aq) = . which is fundamentally a measured quantity because of the coupling of the two measurements.‘.‘(NaHSO. The chosen curve corresponds to y+ = 0.. KY.‘. especially .ENTHALPIES OF SULFITES AND SULFUROUS ACID 429 4.342 kJ mall ’ with the corrections applied.).H&(l). Hi(H.(3669 + 60) J .H&(l) is essentially independent of the choice of yi. solutions it is important to use a self-consistent set of values for y*.. we obtained A. so with no corrections for S.. In this aq) was unchanged. and this independence arises from a group of correction terms in equation (12) mainly the next-to-last term.Hz. As an alternative.mol-‘.HL(l). aq) = .438 kJ. However.‘.Hk(l) = 21.(3670 + 70) J .I. The measurements by Huss and Eckert(*s’ were made at ionic strengths up to I = 0. equations (13) and (15).‘24) we have for comparison: A. Ai. AionHm(H2S03.. aq)] = A.kg-‘.308 kJ.17.O:-(aq) were revealed by a set of calculations in which the presence of S. because the corrections for comparison. and it is useful to examine the relations among the last four series as a check on the consistency of the results and on possible systematic errors.. This value is slightly less than those for the l--l acids given in reference 25.. and Aion Hi(HSO. enthalpy effects were offset by the effects of small changes in the calculated equilibrium composition..2Ai. H:(9) + 2Ai. kg.mol-‘.070) kJ . The different measurements are not entirely independent.O:-(aq) on the calculated equilibrium composition were much smaller and in the same direction as effects on L. in contrast to A.347 kJ.790 at I = 0. On the other hand. charts (3) and (4). To show the influence of the choice of y+. the detailed calculation of the composition of the equilibrium mixtures depends critically on the activity-coefficient function r. With A.HL(l) = 21. aq) is quite sensitive to variation in y*. mol-’ (indirect route) and (21.140) kJ . The agreement between the two routes is excellent.mol-’ and A. mall’ from CODATA.342 + 0.

Thermodynamics 1980. 1015. Golding. were minimal. A. M. A. A. Inorg. Higuchi.430 C. I. C. H. Chem. Can.(l) indicates that errors from traces of 0. Thermodynamics 1983. Chem. Chem. C. E. 9. 6. N. Parker. C. Supplement 2.. Rodenburg. N. Thermodynamics 1974.. N. Waugh. K. Chem.‘.. Vanderzee. Can. A.HL(Na. E. 5. D. J... In the latter series.. and no anomalous temperature drift rates were observed in those series. 103. L.. We shall not present such a comparison here. 63. Zh. in the reaction systems were explored in connection with measurements of AsO. and Johnson”” for sharing their results with us prior to publication. 21. Berg. J. 57. Chem. C.. I12 1. C. Khim. T. S. and possible effects of traces of residual 0. L. 1971. Thermodynamics 1981.. A. J. J.. J. H. 15.. J. 1982.24 -L-0.. and procedures were then developed to minimize O2 effects as much as possible. 441. E. I.. and Johnson’27’ obtained A. Haas. E.S. 1974. E. L. They have included our results in their review and evaluation of a consistent set of properties for the aqueous species and have adopted our values in their calculations. J. W. Hayon. P. 13. 15... Chem. Sot. 44. Haas. Goldberg and Vivian Parker for many stimulating discussions during the evaluation and interpretation of these results and for sharing the results of their calculations with us during the evaluation. I. s). W. O’Hare. L. The agreement strongly indicates that systematic errors are small or else fortuitously cancel. Prikl. von Deuster. 454. 2193. in the experiments. Halow.SO. E. D.. Wagman. B.. V. s) = . 6. J. C. 3. in excellent agreement with our value. 11. Jensen. H.(Na. R. Jensen. H.: Gier. 6.. impurity corrections. 12. 1958. 4. Connick. C. 3711. curves. Nuttall. Examination of the literature for the properties measured in this paper reveals a wide range of values.H... 1960. Churney.(NaHSO. E. 947.: Evans. M. 1972. Ch&. 1979. M. Waugh. E. 14. 27. J. C. We also thank the National Science Foundation for their support through Grant CHE75-22124. J. VANDERZEE AND L. The pattern in chart 3 is most vulnerable to O2 effects. L. P. The effects of traces of 0. R. Falk. Treinin. Schuum. H. 12. Vanderzee. Chem. Am. R. Arkhipova. Chem. Vanderzee.. 94. Sot. J. R. E. 10. T. E. N.. since Goldberg and Parker(26) have recently reported such a review on the properties of aqueous SO. Vanderzee. E. Pitman. J. Il. 17. . 0. L. Tam. Adoption of a different analog curve for L.H. J. C. Vanderzee.. Chistyakova.(13.SO. Vanderzee. Thermo&amics 1974. J. J. and the sulfite ions. Thermodvnumics 1981.. larger amounts of substance were used to reduce possible perturbations. 0. 8. 1. no correlations could be found between deviations of individual values from the mean and ampoule vapor space or other measure of residual Oz. P. We thank Drs O’Hare. R. ReJ: Dafa 1982. Chem. 13. We thank Drs R.O. Bourne. Noll. J. Guthrie. I. 7. Chem. 0. 47. More recently. In the measurements with solid Na. but the close agreement between the direct and indirect routes for A. Chem. chart 1 and table 1. Vanderzee. 1139. M. REFERENCES 1. 13.. Giguere.. Pharm. 36. Bailey. G. Phys Chem. NOLL because of differences among the sets of correction terms. 13.09) kJ mol. Sri. 865. M. 2.) weakens the agreement because the series were run at different ionic strengths and involve different points on the L. Thermodynamics 1981. Wilf.

m. and a-f forms account for 0.8 mass per cent of the b-p form. be used as a good indicator of the anomeric composition of the solid sugars.Hk and those of Stroh and Fincke and of Desai and Wilhoit are not apparent.‘“’ Figure 1 presents the structures of the different ring forms of the sugars. and b-f forms account for 0.‘r3’ -(1050. the initial preponderance of one or two pyranose forms.59) Wilhoit.m. the p-p form predominates and is the more stable anomer.2 and 0. cr-D-pyranose (cc-p) or b-D-pyranose (p-p) slowly diminished and increasing proportions of the furanose forms. Initially. Desai and and Thomas. No discussion is provided by the previous investigators identifying the moisture content.23 + 1.“‘. the b-f. respectively in D-ribose.(1048. solution indicate that crystalline 2-deoxyD-ribose contains at least 98. For both sugars. spectroscopy at 400 MHz and by CP-MAS r3C n. The lack of agreement among the previous determinations for the enthalpy of combustion and formation with our calorimetric measurements as well as the lack of definitive sample characterization by earlier investigators.m. These findings are supported by previous X-ray diffraction and n. kJ . mol. Discussion Our results for the enthalpy of formation of D-ribose at 298. studies indicated that the rates of anomerization of D-ribose and 2-deoxy-D-ribose in mso-d6 solution are sufficiently low so that the proportions of the b-p form and the a-p form have not changed significantly within 120 s of dissolution. the anomeric compositions of crystalline D-ribose and 2-deoxy-D-ribose were investigated by ‘H n. cl-f.‘.15 K can be compared with those of Stroh and Fincke. The results derived from the n.r.H.r is in good agreement with the results of Thomas.‘r2’ -(1062.7 mass per cent.m. Confirmation of the anomeric composition of D-ribose and 2-deoxy-D-ribose was then obtained by direct examination of the crystalline material by CP-MAS 13C n. 0. or precise anomeric distribution in their samples.r.0 mass per cent. The a-p.r.5.r.65) kJ . The extrapolation to zero time of the proportions of the ring forms measured only minutes after the dissolution of the crystalline sugars can. Correspondingly. studies in DMSO-d.4 mass per cent of the u-p form as derived from the DMSO-ds solution results.(r4) .31 f 1.89 + 0.m. (C + H) content.r. Due to the possibility of different sample characteristics. respectively. the sugars were examined as their solutions in dimethylsulfoxide-d.mol-‘.59) kJ. Thus.mol-‘. The crystalline I>-ribose contains 64. spectroscopy.67+ 1. appeared.68) kJ .32+4.4 mass per cent of the b-p form and 35. The n.‘14’ while our -(869. the CP-MAS ‘%Z .r. mol. comparison of the results is not feasible. Therefore. Our .m.66) kJ .A. In agreement with the solution results. in both sugars. spectroscopy at 50 MHz. cl-D-furanose (a-f) or b-D-furanose (b-f). The reason for this difference is also not clear and cannot be accounted for even if we neglect a correction for moisture content. encouraged us to pursue sample identification an extra step. a solvent in which many sugars exhibit a reduced rate of anomerization as compared with corresponding rates in aqueous solution. FOR D-RIBOSE AND 2-DEOXY-D-RIBOSE 439 4.‘14) Reasons for the differences observed between our value for A. mol. mol-’ also differs.0. The only literature value available for 2-deoxy-D-ribose is by Thomas: -(875. (DMSO-de).(1047. therefore. and 0.30) kJ.l. studies.90& 1.

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