O-198

J.

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

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C. E. VANDERZEE

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L. A. NOLL

equilibrium quotient Qn = Kb/&,, where r, is the activity coefficient function for reaction (2) at several ionic strengths. Their results are reported graphically but two numerical values are cited at 298.15 K. 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:-(aq). Connick et a1.4 also made measurements at three other temperatures, from which they obtained A,H,(2) = -4.6 kJ . mol-I. Hayon, Treinin, and Wilfa confirmed Geldings measurements and reported results leading to A,H, = -3.3 kJ mol- at lower ionic strengths. At molalities of HSO; (aq) near 0.02 mol. kg- , the corrections for effects of S,Og- are practically negligible (Z 4 J. mol- ). At higher molalities the corrections can be calculated with sufficient accuracy, and will be described in a later section. Throughout these measurements, as for the dilution studies on Na,SO,(aq), 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. Control of the hydrolysis of SO:-(aq) and ionization of HSO;(aq) is relatively easy and introduces only small correction terms. Corrections for the small amounts of sulfate present in the sulfites are not negligible but are easy to make.

2. Experimental
MATERIALS AND ANALYSES High-purity N, from cylinders was used to provide an N, atmosphere for handling of chemicals and solutions, and also for protection of calorimeter contents. Doubly distilled water was collected and stored under N,. All solutions were prepared and analyzed on a mass basis. Solutions of HCl were standardized against an NaOH solution referred to primary standard potassium hydrogen phthalate. Solutions of (I, + KI) and Na,S,O, were intercompared and referred to KIO, as primary standard. Mass-buret techniques were used for all analyses. Molar masses of KIO,, Na,SO,, and Na,S,O, were taken to be 214.005, 126.042, and 190.105 g. mol- , respectively. Na,SO,(s), Baker and Adamson, and Na,S,O,(s), Mallinckrodt AR, lot YRP, were used as received. The solids were assayed for sulfite content by transferring a measured mass of sample under N, into an excess of air-free (I2 + KI) solution and back-titrating the excess I, with standard Na,S,O, and starch indicator.t3 The solids were assayed for sulfate by gravimetric procedures.3 Samples (about 1 g) were dissolved on hot air-free HCl, the solutions were boiled to expel SO,, and BaSO, was precipitated by addition of BaCl, solution. Samples of Na,SO,, when heated, had small changes in mass corresponding to about 0.1 mass per cent of H,O. In another procedure, samples of the solids were placed in tubes which could be heated in an oven. Dry N, was passed through the tubes and then through an absorber containing CaSO,. +H,O to collect the entrained H,O. This procedure indicated (0.09+0.02) mass per cent of H,O in the Na,SO,(s) samples and (0.12+0.02) mass per cent of H,O in the Na,S,O,(s) samples. The Na,SO,(s)

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samples assayed (99.2,+0.2,) mass per cent of Na,SO,, (0.63 kO.05) mass per cent of Na,SO,, and (0.09+0.02) mass per cent of H,O. The Na,S,O,(s) samples assayed (66.25 kO.08) mass per cent of SOZ, (1.55 kO.02) mass per cent of Na,SO,, and (0.12 kO.02) mass per cent of H,O. These results were interpreted as Na,SO,: (1.55kO.02) mass per cent, Na$,O,: (98.2,+0.1,) mass per cent, Na,SO,: (O.lOf0.08) mass per cent, and H,O: (0.12+0.02) mass per cent.
CALORIMETRIC EQUIPMENT AND PROCEDURES

The solution calorimeter has been described previously!- and its performance has been monitored for several years. (12) The jacket (thermostat) temperature was controlled to 13 x 10e4 K. 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, and were recorded by a digital printer. Corrected temperature changes were evaluated by standard procedures 3*14) and programs adapted for quartz thermometry. All of the results refer to the isothermal calorimetric process at 298.15 K, and were referred to this reference temperature (0,) by the equation:314) (3) in which ci and sf are the electrical energy equivalents determined for the initial and final states of the process, 0, and 0, are the calorimeter temperatures at the beginning and end of the main period, and A@, is the temperature-change correction for stirring and heat exchange. Because of possible perturbing effects from oxidation of sulfite by traces of oxygen during the runs, temperature-drift patterns and thermal moduli were monitored closely for evidence of such perturbations and needed corrections, following procedures outlined in reference 14. In most runs, operating patterns were normal. Calorimetric samples were weighed into 10 cm3 glass ampoules under N, with minimal exposure to air, and the ampoules were sealed with a Teflon plug and wax seal. The ampoules were mounted in the sample holder and then the empty calorimeter vessel was attached. The empty assembly was purged with N, for several minutes, and then the calorimetric solution was transferred into the vessel from a 1.06 dm3 delivery bulb which could be weighed before and after delivery. A slow stream of N, (0.2 to 0.3 cm3. s-) was maintained into the calorimeter through a chimney vent during delivery of the calorimetric solution and during the run. 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). 3. Reaction
STANDARD ENTHALPY OF SOLUTION

A,H = E~(O~-O~)+E~(O~-O~)+(E)AO,,

patterns and results

OF SODIUM SULFITE

Chart 1 represents the network of processes leading to As0rH~(Na2S03, s). The small amount n3 of NaOH was added to suppress hydrolysis of SO:-(aq): a

420
n, Na,SO,

C. E. VANDERZEE

AND L. A. NOLL

CHART 1 n,Na,SO,(s)

n,NaOH (n, +n,)Na,SO,

.(n,+n,)Na,SO,.

AH,0

I n3 NaOH (nl + n,)Na,SO,

(n2 + n,)Na,SO,

coH,O

molality of 0.005 mol. kg - is adequate. A small amount n4 of Na2S03 was needed to scavenge residual traces of 0, from the solvent before dissolution occurs. The solid sample contained a small fraction n2/n1 of Na$O,(s) which was assumed to be present as a separate phase in the solid mixture. The ratio n5/n4 may be larger than n2/n1 due to oxidation of sulfite by residual oxygen in the solution, but since we can take L, for Na,SO, to be equal to L, for Na,SO, with sufficient accuracy, the dilution corrections involve only the sums (n4 + n5) and (nl + n,), which are not changed by the reaction with residual O2 in the solution. The approximation that L+(Na,SO,) = L,(Na,SO,) was also used in the evaluations3 of L+(Na,SO,), so the effects of the approximation are practically nullified in the calculation of Aso,Hi. From chart 1, with L+(Na,SO,) = L,(Na,SO,), n, Aso,Hi(Na$O,, -(nl s) = Ar H + (n., + n,)Li(Na,SO,) +n, +n,+n,)Li(Na,SO,)+ - n2 As,,,Hi(Na,SO,, s) n,{L$(NaOH)-L!&NaOH)}. (4)

In applying equation (4), the values of L, were taken for the components at the ionic strength of the mixture, 3, and the enthalpy of mixing or unmixing at constant ionic strength was taken to be zero. (r3) This rule was followed in all of the calculations in this paper. The superscripts i and f refer to the initial and final states, respectively, and the isothermal calorimetric process is identified with A,H. For Na,SO,(s), Aso,Hm = 2.43 kJ. mol- .(15) Values of L,(NaOH) and other uniunivalent electrolytes used in this work were taken from Parkers compilation.16 Table 1 represents the experimental results for chart 1 and the standard process: Na,SO,(s) + coH,O(l) = Na,SO, . coH,O; A,,,Hm(Na2S0,, s) = -(13.2640.06) kJ.mol-. (5)

The uncertainty interval includes estimates of contributions from systematic errors in the terms in equations (3) and (4). The contributions from terms in equation (3)

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TABLE 1. Experimental results leading to A~,,H~(Na,SO,, s, 298.15 K). Symbols correspond to chart 1 and equation (4). with M, representing the molar mass of H,O. Sulfate content is obtainable from the ratios n&r, = n&t, = 0.0056,
4 n4 n3 AM E kg

mol 0.045435 0.039761 0.039832 0.044733

0.042292

mol 0.020752 0.066187 0.10595 0.020800

0.065533

mol 0.005834 0.005834 0.005834 0.005834

0.005834

AH -L J -539.5, -476.3, -487.7,

-535.3,

ho,H: kJ.mol- - 13.24 - 13.26 - 13.34

-13.33

0.040239 0.041954 0.040506 0.039760

0.10783 0 0.041954 0.082461

0.005834 0.005834 0.005834 0.005834

1.0655 1.0655 I .0655 1.0645 1St645 1.0645 1.0669 1.0669 1.0669

- 506.2, -490.7, -512.5, -479.9,

-480.3,

13.26 13.23 13.42 13.20

-13.25

a Not included in the mean. Mean k 2~7,. for 8 runs: - (13.26 + 0.04) kJ mol - ; uncertainty interval: kO.06 kJ molt

are estimated to be: from E, 0.02 per cent or 1 J. K- ; from (0, - O,), 3 x lo- K; A@,, 6 x IO- K. The major contribution from equation (4) is that from L+(Na,SO,), estimated at 40 J. mol-. From a series of 8 runs with we obtained made n4 = 0, A.,,,Hi(Na,SO,, s) = -(13.54&0.07) kJ.mol- for the mean+2c,. This result was more negative than the result from the series in table 1, and is most likely so because of residual traces of O2 in the calorimetric solvent. The excess enthalpy amounts to 11 J * kg- of solution. Oxidation of sulfite to sulfate by oxygen releases about 566 kJ * mol- of 0,. This would indicate a residual oxygen content of about 1.9 x lo- 5 mol. kg- in the diluent solution. For the series with n4 = 0, made earlier than the series in table 1, there were some runs with strong linear perturbations of drift rates,14) whereas for the series in table 1, made with more thorough exclusion of 0,, drift-rate perturbations were small. The procedures outlined in reference 14 were developed partially in connection with these runs.
THE STANDARD ENTHALPY OF IONIZATION OF HSO;(aq)

The quantity AionHi(HSO;, protonation reaction:

aq) is obtained

from a calorimetric

study of the
(6)

SO;-(aq)

+ H+(aq) = HSO,(aq),

for which the appropriate flow-chart is represented by chart 2. As in chart 1, the initial and final mixtures can be regarded as independent solutions of each component, each in the hypothetical-ideal standard state without ionization or hydrolysis of the anions. In the buffered calorimetric solutions, with initial molalities m2 z 2m, z 0.02 mol. kg- and the final ratio (nl +n3)/(n2 +n,) z 2, the ratio n(H,SO, +SO,)/n(HSO;) is less than 0.0001 and there is no significant

422

C. E. VANDERZEE CHART n, HCI ceH,O

AND 2

L. A. NOLL

n,Na,SO,n,NaHSO,n,Na,SO,.

zH,O

n, HCI

AH,0

n,Na,SO,

.n,NaHSO,.n,Na,SO,.EH,O

ArH

i; n,NaCI.(n,-n,)Na,SO,.(n,

+n,)NaHS03~n,Na,S0,~(A+B)H,0

n,NaCI.(n,-n,)Na,SO,(n,

+n,)NaHSO,

n,Na,SO,~

mH,O

hydrolysis of SO: - or SO:-.

Then from chart 2.

-n,Ai,,Hi(HSO;, aq) = A,H +n,{Lk(Na,SO,) - L:(Na,SO,)} + n2{ L$(Na,SO,) - L$(Na,SO,)) n3{L; (NaHSO,) - L$ (NaHSO)) +n,{Lk(HCl)-Li(NaCl)+ L$(Na,SO,)-L$(NaHSO,)}.

(7)

Again we took L,(NaSO,) = L,&Na,SO& to be consistent with approximations made in evaluating L+(Na,SO,). (3) The dilution term involving Na,SO, is practically negligible because n,/n, is small and L+(Na,SO,) changes by only a small amount at the ionic strengths used in this work. We estimated L,(NaHSO,) = L,+(NaHC03) at these ionic strengths, (I) based on the observation that L,(Na,SO,) is only slightly larger than L+,(Na,C03),3* I which strongly implies a close similarity in L, for NaHSO, and NaHCO,. The influence of Na$,O, from the equilibrium, reaction (2) requires evaluation of the relative apparent molar enthalpy for the equilibrium state, represented by L;. Following procedures outlined elsewhere,14* ) we obtain L;(NaHSO,) = (1 -a)L,&NaHSO,)+(a/2){L+(Na,S,O,)+A,H~(2)},
(8)

in which CI is the fraction of HSO, converted to S,OzP, and is evaluated from K(2) = Qu = 0.045 kg. mol- from the results of Connick et ~1.~ We estimated L,(Na,S,O,) = L@(Na,SO,) by analogy. There are few similar electrolytes to use as analogs. The value of A, H:(2) = - 4.2 kJ . mol- was found by applying estimated dilution corrections to the values of ArH, measured by Connick et ~1.~ and by Hayon et al.*) The corrected results from the two sources were in good agreement. The primary term in the correction from L, to Lz arises from A,Hk(2). In equation (7) the total correction for Na,S20, in the mixture affects Ai,,Hk(HSO;) by

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TABLE 2. Experimental results leading to AiO&(HSO;, 298.15 K). Symbols correspond to chart 2 and equation (7), with M, representing the molar mass of H,O AM.
n2

n,
mol 0.010525 0.010564 0.010711 0.010475 0.010532 0.010686 0.010727

nA

BM,

AJ
J 16.05 15.45 16.48 16.63 12.74 13.98 14.07

kg
0.011053 0.010593 0.010801 0.010948 0.009836 0.010063 0.010076 0.01065 0.01021 0.01041 0.01055 0.00948 0.00970 o.cQ971

mol 0.020911 0.021125 0.021219 0.021214 0.021526 0.031509 0.021515

mol 0.000229 0.000231 0.000233 0.00023 1 0.000273 O.OCKI235 0.000235

kg
1.0582 1.0596 1.0578 1.0583 1.0596 1.0592 1.0596

A,,H:WSO; kJ,mol- -3.660 -3.667 -3.736 -3.726 -3.517" -3.610 -3.616

Not included in the mean. Mean + 20,. for 6 runs: A,,, HL(HSO;.

aq) = - (3.669 + 044) kJ mol.

6 J.mol-. The uncertainty in the estimate of L,(NaHSO,) is estimated as +30 J.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. Errors in n2 and n3 arising from uncertainties in the assays of the solid samples have negligible influence on the corrections. Table 2 contains the experimental results leading to: Aio,H~(HSO;, aq, 298.15 K) = -(3.66,f0.06,) kJ*mol-, (9)

for the mean and uncertainty interval. Most of the runs had temperature-drift patterns close to normal, with only small linear perturbations in the after-periods for the reaction,(4) and presented no special problems in evaluating the heatexchange corrections.4 The uncertainty interval was evaluated as for reaction (5). Under the handling procedures followed in this work, residual oxygen in the ampoule solution should have produced an error of 10 J. mol- or less in Aion HL. Run 5, which was omitted from the mean, was suspected of having a much larger amount of oxygen in solution.
THE STANDARD ENTHALPY OF SOLUTION OF SODIUM METABISULFITE

One reaction of interest is (10) which can be combined with the ionization of H,O(l) and HSO;(aq) to yield reaction (1). The flow-chart for reaction (10) differs only slightly from chart 1: (1) the solid sample is n,Na,S,O, * n,Na,SO, . n,Na,SO,(s), with each compound treated as a separate phase; (2) a slight excess of NaOH is used, and the amount remaining in the final state is (n3 - 2n,). Then
n, AHL(10) = A,H(lO)-n,A,,,Hk(Na,SO,,

Na,S,O,(s)

+ 2NaOH(aq)

= 2Na,SO,(aq)

+ H,O(l),

s)-n,A,,,Hz(Na,SO,,

s) (11)

+(n,+n&,(Na,SO,)+n,Lk(NaOH) -(2n,+n,+n,+n,+n,)LfQ(Na,SO,)-(n,-2n,)Li(NaOH),

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TABLE 3. Experimental results leading to A&(10) for Na,S,O,(s)+ZNaOH(aq) ZNa,SO,(aq)+H,O(l)). Symbols correspond to equation (1 I), with AM, being the mass of H,O in the calorimeter initially. Quantities n2, ngr and n6 can be calculated from the ratios: nz/n, = 0.021 I,, n.Jnl = 0.0015,: n5/n4 = 0.0056, - nl mol 0.025939 0.027655 0.026583 0.027391 0.027146 0.025901 0.026087 Mean: AWlO) n3 mol 0.059077 0.062433 0.060606 0.061303 0.061218 0.059229 0.061465 = -97.61 kJ,mol-;

%
mol 0.020259 0.020720 0.020805 0.020783 0.020751 0.020748 0.020737 2a, = 0.07 kJ.mol-

AM, kg 1.1109 1.1148 1.1121 1.1134 1.1137 1.0973 1.1133 I; uncertainty

W
J -2485.2 -2656.5 - 2548.6 - 2630.0 - 2604.3 -2481.2 - 2502.8 interval: k0.10

A,ff,( 10) __---kJ.mol- -97.50, -97.72, -97.57, -97.68, -97.63, -97.50, -97.63, kJ. mol-1.

and, as in equation (4), L+(Na,SO,) is taken equal to L,(Na,SO,) in the mixtures. Table 3 presents the experimental results. The first two correction terms in equation (11) are relatively small. Errors in the assay of the solid sample of Na,S,O, affect mainly the terms in n, and n6, and are largely compensatory insofar as the corrections are concerned, and partially compensatory with respect to A,Hi(lO). Consideration of estimated contributions leads to 0.10 kJ. mol- l for the uncertainty interval for AHk(10). Thus, A,Hg(lO) = -(97.61 fO.lO) kJ.mol-. A direct approach to reaction (1) requires the dissolution of the Na,S,O,(s) in a dilute acid solution to control hydrolysis of HSO;(aq), and usually results in formation of small amounts of H,SO,(aq). The corrections become more complex than for dissolution in NaOH(aq), but enough information is available for them to be made. Chart 3 shows the set of processes leading to A,Hg(l). To simplify the corrections, no sulfite was added to the calorimetric solution, but the HCl solution was deoxygenated by sparging with high-purity N, and was carefully protected from 0, during all operations. In blank calorimetric experiments, in which a small amount of sodium solution was added to the acid solution, the thermal response indicated that the 0, concentration was at acceptably low limits. From chart 3, the standard enthalpy change A,H,Yj,(l) is given by: n,A,HL(l) = ArH-n,A,,,H~(Na,SO,)-n,A,,,H~(Na,SO,)+n,L+(HCl) - (2n, + n&2 (NaHSO,) - n,Li(Na,SO,) - n,Li(NaCl) -(n3 -n,)L~(HCl)+x{L~(NaHSO,)-Li(NaC1) + Li(HCl)} + z{ Li(Na,S04) - Li(NaHS0,) - Li(NaC1) + Li(HCl)) + n,Ai,,Hz(HSO;) + X{AionH;a(H2S03) -Li(H,SO& +zAionH;(HSO;).

(12)

The experimental results for this route are given in table L+,(NaHSO,) = L+(NaHCO,) as an adequate approximation. The term is that involving ionization of H,SO,, for which (AionH~(H2S03)-Li(HzS03)} = -(17821 f 180) J.moll separately at essentially the same ionic strengths (I z 0.09 to

4. We can take largest correction the combination was measured 0.12 mol. kg- ).

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n,Na,S,O,n,Na,SO,.n,Na,SO,(s)

n,HCI. mH,O

n,HCI.(A+n,)H,O

((2n, +n,-x)NaHSO,+xH,SO,+(n, -z)Na,SO,+zNaHSO,+(n,+x+z)NaCl +(n,-n,-x-z)HCI}.AH,O

j(2n, +n,-x)NaHSO,

+xHzSO, +(n:-z)Na,SO,+zNaHSO,+(n,+x+z)NaCI +(n,-n,-x-z)HCI}.mH,O I

1

j2n,NaHSO,+n,NazSO,+(nzNa,SO,+n,HCI)}~coH,O

Equation (12) then yields a value of A,Hk(t) which is independent of the value assigned to L,(H,SO,). The uncertainty of _+180 J. mol- contributes +30 J. mol- to the uncertainty in AH:(l), since x/n1 x l/6. Calculation of the composition variables x and y requires values of the ionization constants KT for H,SO,(aq) and Kz for HSO;(aq), together with the corresponding activity-coeffocient functions r, and r,: m(H+)m(HSO~)/{m(H2S0,)m) m(H+)m(SO~-)/(m(HSO,)m] = KY/T,; = Kz/T,. (13)

(14)

TABLE 4. Experimental results leading to Ar,,Hm(l) for reaction (1): Na,S,O,(s)+H,O(t) = 2NaHSO,(aq). Symbols correspond to equation (12) and chart 3, with M, being the molar mass of Hz0
nI I;;;;i % n2 n3 AM _4H &H;(l)

- ..-._ --_. 0.050330 0.050869 0.061675 0.057946 0.058892 0.055271

mol 0.000078 0.000078 o.oooQ95 O.OOtKt89 o.ooucl91 O.OC0085

i&i 0.001063 0.001074 0.001303 0.001224 0.001244 0.001167 kJ,mol-;

-~--..-0.011307 0.011646 0.011275 0.011569 0.011343 0.011622

mol

kg --.1.1378 1.1719 I.1346 1.I641 1.1414 1.1695

J 1254.3 1271.6 1509.8 1432.4 1447.6 1368.5

kJ.mol21.313 21.333 21.362 21.366 21.344 21.334

Mean _i 2u,: (21.342+0.016)

uncertainty interval: 170 J.mol-

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In our mixtures, the amount of SOiand OH-(aq) are negligible. For H,SO, solutions, Huss and Eckert recently reported KY = (0.0139 & 0.0002) at 298.15 K. together with the related activity-coefficient function f,. Their value of K; is strongly supported by those of Britton and Robinson,) Ellis and Anderson,20 and Devese and Rumpf. (21) Other values22*23 fall into close agreement with KY = 0.0139 when recalculated with the common values of r, from Huss and Eckert. At the low ionic strengths used in our work, values of KY/T, based on Huss and Eckerts work should be valid for our mixtures and should provide a quite reliable basis for calculation of X. Huss and Eckert present their results for the activity coefficients I* = r,j2 by a graph, but do not present an unambiguous combination of the parameters in the equation: In y+ = - A(I/m)/{ 1 + B(I/m)2} + C(Z/mO), (13 to correspond to their figure 3. Consequently we evaluated I* directly from the measured results in their table II. Our evaluations could be represented by equation (15) with B = 1.643 and C = 0.09, with the Debye-Hiickel parameter A = 1.176, and m = 1 mol. kg-. In the above calculations, Huss and Eckerts results lead directly to r, = y:/yo, with the usual approximation that y. = 1 for the neutral species in equation (13). For HSO,(aq) we used the value K = 0.0105 based on CODATA selections24 and used r, = Z-f as an estimate for r,. For our mixtures, K/T, ranged from 0.0221 to 0.0228 and K/T, from 0.0265 to 0.0283. At equilibrium in these mixtures, z/x z 0.01, so the estimation of r, introduces little error. A 10 per cent error in z would contribute an error of about 4 J. mall. The error in x should be no more than 1 per cent and contribute no more than 30 J. mol- to the error in A,H;(l). The other major contributor is L?(NaHSO,), evaluated by equation (8), with c( based on K, = 0.048 kg. mol- at these ionic strengths. Here the correction for S,O:ranged from 29 to 36 J. mol-. The uncertainty interval given in table 4 includes these among other estimated terms. Thus, A,H;(l) = (21.342kO.07) J*moll.
STANDARD ENTHALPY OF IONIZATION OF H,SO,(aq)

Measurement of Ai,,H~(H,S03, aq) is complicated because H,SO,(aq) is a relatively strong acid (KT = 0.0139),(s so its solutions are a mixture of H,SO,(aq) and HSO;(aq). Then for calorimetric studies of the reaction: H,SO,(aq) = H+(aq) + HSO;(aq),
(16)

or the reverse (protonation) reaction, 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, equation (13), with similar calculations for the sulfate impurity and the process: HSO;(aq) = H+(aq) + SOi-( (17) which also contributes to the calorimetric response. The calculation of solution composition before and after the calorimetric process is the same as for the final mixture in chart 3.

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CHART 4 jn,NaHSO,+n,Na,SO,+(n,-n,)HCI+n,NaCl} ccH,O n,HCI .xH,O

[(n,-x)NaHSO,+xH,SO,+(n,-z)Na,SO,+zNaHSO, +(n,+.x+z)NaCl+(n,-n,-x-z)HCl}.mH,O

{tno -.x)~aHS0, +xH,SO, +(n, -z)Na$O, +(n,+x+z)NaCl+(n,-n,-x-z)HCI}~AH,O ~ ..

+zNaHSO., /,/n,HCI~BH20

A? 7

((n,-y)NaHSO,+yH,SO,+(n,-~)Na,SO,+zNaHSO,+(n,+y+i)NaCl +(n,+n,-n,-y-z)HCI}.(A+B)H,O

((n,-))NaHSO,+yH,SO,+(n,--;)Na,SO,+,-NaHSO,+(n,+y+,-)NaCI +(n,+n,-n,-y-z)HCI.coH,O

I {n,NaHSO,+n,Na,SO,+(n,+n,-n,)HCl+n,NaClj~H,O

Chart 4 outlines the network of correction steps for a calorimetric study of the protonation of HSO;(aq). A substantial excess of NaHSO, helps to increase the amount of added H+(aq) consumed in the protonation. A very efficient procedure is to use the final calorimetric solution from chart 3 as the initial calorimetric mixture for chart 4. This was done by using two ampoules in the multiple ampoule holder. ) The first ampoule was filled with the solid sodium metabisulfite and the second with 2.667 mol. kg- HCI solution. Electrical calibrations were made before and after each reaction step. These procedures reduce the experimental time and avoid transfer of oxygen-sensitive solutions. Computational time is reduced since the last two steps in chart 3 are the reverse of initial steps in chart 4. To maintain the close relations between charts 3 and 4 and tables 4 and 5, the same symbolism is used, except that n, = Zn, +n,. Calculation of .v and Z followed the same procedures as for x and z. The ionic strength changes by only a small amount in the calorimetric process, so KY/T, and Ki/T, differ by only small amounts between initial and final states. The relative apparent molar enthalpies f,+ change by only a small amount as well, so the dilution corrections have several small difference terms. As written, the overall value of AH for chart 4 is zero. Collection and

428 rearrangement

C. E. VANDERZEE

AND L. A. NOLL

of terms leads to the relation:

(~-~){A~~~H~(H~SO,)-LO(H~SO~)) = -A,H-(z-~)A~,,H~(HSO;) + n,{L; (NaHSO,) - L; (NaHSO,)} + n,(LiNa,SO,) - L$,(Na,SO,)} +n,{L;(HCI)L;(HCl)} +n,{L;(HCl)-L$4(HC1)] + n,{Li(NaCl) - L$(NaCl)} + x{L; (NaHSO,) + La(HCl) - L$(NaCl)} + y{ Lt(NaC1) - Li(HC1) - L; (NaHSO,)} + z(L+(HCl) -L$NaCl) + L$Na,SO,) - L$(NaHSO,)} + z{Li(NaCl) - Li(HC1) + Lt(NaHS0,) - Li(Na,SO,)}, (18) in which (y-x) is the extent of protonation of HSO;(aq) in the process. Values of L,(H,SO,) are not available, but are probably small. For comparison, L,JH,CO,) would be about 45 J. mol- at these ionic strengths. Our first approach is to isolate and evaluate the combination: (Aion Hi(H,SO,)L+(H,SO,)), with the approximation that L,(H,SO,) is essentially constant for our range of ionic strengths. This is then the combination term needed for equation (12) to calculate A,Hk(l). At some later time, when L,(H,SO,) becomes available, AionHi(H2SOJ) can be obtained from our results. To a first approximation, many may choose to set L+(H,SO,) = 0, since it will be quite a small term. Table 5 contains the experimental results. The precision of the resultant values of is good, considering the number of corrections {AionH~(H2S03)-L~(H2S03)} which must be made. The error in (y-x) should not exceed 1 per cent, since Huss and Eckerts values* of KY and I-, are closely correlated in their evaluation. The next largest estimated error is + 60 J. mol- r from the uncertainty in L+(NaHSO,). At our ionic strengths, L,(NaHSO,) should be close to its maximum, estimated at (285+30) J.mol-, with the difference term (Li -Lb) z (0 f 10) J. mol-. The estimated uncertainty interval, f 180 J . mol- , includes these and other smaller estimated errors. The sulfate impurity correction is appreciable but leaves no significant error. With the approximation that L,(H,SO,) = 0, we have AionHz(H2S03, aq) = -(17.82+0.18) kJ.mol-. (19)

TABLE

5. Experimental results leading to (A,,,&--L+)(H,SO,). Symbols correspond to chart 4 and equation (17), with M, being the molar mass of H,O, and with n6 = O.O0077n,
n2 n3 AM, n4

mol 0.10074
0.10182 0.12345 0.11598 0.11787

mol 0.001063
0.001074 0.001303 0.001224 0.001244

mol 0.011307 0.011646

0.011275 0.011569 0.011343

kg 1.1378 1.1719
1.1346

mol 0.027514 0.026175

0.025726 0.025711 0.022888

EM I

kg 0.01032 0.00981
0.00965 0.00964 0.00858 0.00989

A,H J 270.8, 260.40 276.7, 270.6& 244.20 269.7,

&,.H:-L&HW,)

kJ.mol-
-17.760 -17.896 -17.801 -17.901 -17.814 -17.755

1.1641
1.1414

0.11063 f 180 J.mol-r.

0.001167

0.011622

1.1695

0.026381

(A.,.Kt, - L&H,SO,):

Mean f 2a,:

-(17.82, +0.05,) kJ.mol-;

uncertainty

interval:

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4. Discussion
In the evaluation of terms in equations (12) and (18), the detailed calculation of the composition of the equilibrium mixtures depends critically on the activity-coefficient function r,, equations (13) and (15). The measurements by Huss and Eckert(*s were made at ionic strengths up to I = 0.055 mol. kg- , so it is necessary to adopt a function such as equation (15) for extrapolation to the range 0.094 to 0.118 mol. kg- for our solutions. We retained their choice for the ion-size parameter and used guidance from analog curves for similar l-l electrolytes25 in selection of the linear term Cl in equation (15). The chosen curve corresponds to y+ = 0.790 at I = 0.1 mol.kg- . This value is slightly less than those for the l--l acids given in reference 25, but is probably more suitable for a mixture in which the primary cation is Na +(as). To show the influence of the choice of y+, calculations were also made for a curve corresponding to I = 0.1 mol.kg-. ye = 0.829 at These yielded: AionH~(H2SOJ, aq) = - 17.438 kJ.mol- and A,HL(l) = 21.347 kJ.mol-. This comparison reveals that A,H&(l) is essentially independent of the choice of yi, and this independence arises from a group of correction terms in equation (12) mainly the next-to-last term, which is fundamentally a measured quantity because of the coupling of the two measurements, charts (3) and (4). On the other hand, AionHm(H2S03, aq) is quite sensitive to variation in y*, so in calculating dilution corrections on H,SO, solutions it is important to use a self-consistent set of values for y*, KY, and Ai,,Hz. The effects of the corrections for the formation of S,O:-(aq) were revealed by a set of calculations in which the presence of S,O:-(aq) was omitted. In this aq) was unchanged, because the corrections for comparison, Ai,,Hk(H2S03, enthalpy effects were offset by the effects of small changes in the calculated equilibrium composition. However, in the calculation of A,H&(l), the effects of S,O:-(aq) on the calculated equilibrium composition were much smaller and in the same direction as effects on L;(NaHSO,), so with no corrections for S,O:-(aq), we obtained A,Hk(l) = 21.308 kJ.mol-, in contrast to A,HL( 1) = 21.342 kJ mall with the corrections applied. The uncertainty in the S,O:-(aq) corrections should be no more than 10 J. mol. Other sources of error have been discussed with the presentation of results. The different measurements are not entirely independent, however, 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. A value of A,Hk(l) can be calculated indirectly from the combination: {A, H:(9) + 2Ai,, Hi(H,O) - 2Ai,,Hm(HSO;, aq)] = A,HL(l). With A,,,Hk(H,O) = (55806+40) J. mall from CODATA,24) we have for comparison: A,Hk(l) = (21.340+0.140) kJ . mol- (indirect route) and (21.342 + 0.070) kJ . mol- (direct route). As an alternative. the comparison can be expressed as: AionHz(HSO;, aq) = - (3670 + 70) J . mol- I. and Aion Hi(HSO;, aq) = - (3669 + 60) J . mol- . The uncertainty interval for the indirect route takes into account some partial compensation of errors in the ditition corrections and the other correction terms. The agreement between the two routes is excellent, especially

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C. E. VANDERZEE

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L. A. NOLL

because of differences among the sets of correction terms, impurity corrections, and possible effects of traces of residual 0, in the experiments. Adoption of a different analog curve for L,(NaHSO,) weakens the agreement because the series were run at different ionic strengths and involve different points on the L, curves. The agreement strongly indicates that systematic errors are small or else fortuitously cancel. The effects of traces of 0, in the reaction systems were explored in connection with measurements of AsO,HL(Na,SO,, s), chart 1 and table 1. and procedures were then developed to minimize O2 effects as much as possible. In the measurements with solid Na,S,O,, no correlations could be found between deviations of individual values from the mean and ampoule vapor space or other measure of residual Oz. In the latter series, larger amounts of substance were used to reduce possible perturbations, and no anomalous temperature drift rates were observed in those series. The pattern in chart 3 is most vulnerable to O2 effects, but the close agreement between the direct and indirect routes for A,H;(l) indicates that errors from traces of 0, were minimal. Examination of the literature for the properties measured in this paper reveals a wide range of values. We shall not present such a comparison here, since Goldberg and Parker(26) have recently reported such a review on the properties of aqueous SO, and the sulfite ions. 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. More recently, OHare, Jensen, and Johnson27 obtained A,,,H;(Na,SO,, s) = - (13.24 -L-0.09) kJ mol- , in excellent agreement with our value. We thank Drs R. N. 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. We thank Drs OHare, Jensen, and Johnson for sharing their results with us prior to publication. We also thank the National Science Foundation for their support through Grant CHE75-22124.
REFERENCES
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. Falk, M.; Giguere, P. A. Can. J. Chem. 1958, 36, I12 1. Guthrie, J. P. Can. J. Chem. 1979, 57, 454. Vanderzee, C. E.; Noll. L. A. J. Chem. Thermodynamics 1983, 15, 1015. Connick, R. E.; Tam, T. M.; von Deuster, E. Inorg. Chem. 1982, 21, 103. Golding, R. M. J. Chem. Sot. 1960, 3711. Arkhipova. G. P.; Chistyakova, I. I. Zh. Prikl. Khim. 1971, 44. 2193. Bourne. D. W. A.; Higuchi, T.; Pitman, I. H. J. Pharm. Sri. 1974, 63, 865. Hayon, E.; Treinin, A.; Wilf, J. J. Am. Chem. Sot. 1972, 94, 47. Vanderzee. C. E.: Gier, L. J. J. Chem. Thermodynamics 1974, 6. 441. Vanderzee, C. E.; Rodenburg, M. L. N.; Berg, R. L. J. Chem. Thermo&amics 1974, 6. 17. Vanderzee, C. E.; Waugh, 0. H.; Haas, N. C. J. Chem. Thermodynamics 1980, 12. 27. Vanderzee, C. E.; Waugh, 0. H.; Haas, N. C. J. Chem. Thermodynamics 1981, 13. 1. Vanderzee, C. E. J. Ch&. Thermodynamics 1981, 13, 947. Vanderzee. C. E. J. Chem. Thermodvnumics 1981. 13. 1139. Wagman, 0. D.: Evans, W. H.; Parker, V. B.; Halow, I.; Bailey, S. M.; Schuum. R. H.; Churney. K. L.; Nuttall, R. L. J. Phys Chem. ReJ: Dafa 1982, Il. Supplement 2.

A,H;

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AND

2-DEOXY-D-RIBOSE

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4. Discussion
Our results for the enthalpy of formation of D-ribose at 298.15 K can be compared with those of Stroh and Fincke,r2 -(1062.32+4.65) kJ . mol- , Desai and and Thomas,(r4) - (1048.89 + 0.59) Wilhoit,r3 -(1050.90& 1.59) kJ.mol-, kJ . mol- l. Our - (1047.23 + 1.66) kJ . mol- r is in good agreement with the results of Thomas.14) Reasons for the differences observed between our value for A,Hk and those of Stroh and Fincke and of Desai and Wilhoit are not apparent. No discussion is provided by the previous investigators identifying the moisture content. (C + H) content, or precise anomeric distribution in their samples. Due to the possibility of different sample characteristics, comparison of the results is not feasible. The only literature value available for 2-deoxy-D-ribose is by Thomas: -(875.67+ 1.30) kJ.mol-,14 while our -(869.31 f 1.68) kJ . mol- also differs. The reason for this difference is also not clear and cannot be accounted for even if we neglect a correction for moisture content. 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, encouraged us to pursue sample identification an extra step. Therefore, the anomeric compositions of crystalline D-ribose and 2-deoxy-D-ribose were investigated by H n.m.r. spectroscopy at 400 MHz and by CP-MAS r3C n.m.r. spectroscopy at 50 MHz. Initially, the sugars were examined as their solutions in dimethylsulfoxide-d, (DMSO-de), a solvent in which many sugars exhibit a reduced rate of anomerization as compared with corresponding rates in aqueous solution. For both sugars, the initial preponderance of one or two pyranose forms, cr-D-pyranose (cc-p) or b-D-pyranose (p-p) slowly diminished and increasing proportions of the furanose forms, cl-D-furanose (a-f) or b-D-furanose (b-f), appeared. The n.m.r. 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 extrapolation to zero time of the proportions of the ring forms measured only minutes after the dissolution of the crystalline sugars can, therefore, be used as a good indicator of the anomeric composition of the solid sugars. The results derived from the n.m.r. studies in DMSO-d, solution indicate that crystalline 2-deoxyD-ribose contains at least 98.8 mass per cent of the b-p form. The a-p, cl-f, and b-f forms account for 0.5, 0.0, and 0.7 mass per cent, respectively. The crystalline I>-ribose contains 64.4 mass per cent of the b-p form and 35.4 mass per cent of the u-p form as derived from the DMSO-ds solution results. Correspondingly, the b-f, and a-f forms account for 0.2 and 0.0 mass per cent, respectively in D-ribose. Thus, in both sugars, the p-p form predominates and is the more stable anomer. These findings are supported by previous X-ray diffraction and n.m.r. studies.. Figure 1 presents the structures of the different ring forms of the sugars. 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.m.r. spectroscopy. In agreement with the solution results, the CP-MAS %Z