On the use of dilution calorimetry in the study of hydrogen-bonding self-association reactions: benzoic acid in benzene

AND

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C'etlti.c, tl'AppIic~ciiioti C~i/oi.itrrc;ti.ic~ T l ~ e ~ ~ i t ~ o c l ~ t ~ c iD6pcii.tc'irretzt tie c.l~i~t!ic,, ell et tt~ic~iir, L1tlii.c,raiic; tie SIrci.hi.ooXc~, SI~c,i-hrooX(, (Qoc;.).Ccii~ciclei .Ilk' 2RI TRICHUK KRISHSAS,WAYYE ~ K L T O N E R SAULGOLDMAN, JEA>-LUC C DU , and FORTIER. Can. J. Chem. 59.530 (1979). A calorin~etricdilution method was applied to the system benzoic acid in benzene at 25C. Trio different calorimeters, a batch calorimeter (at Guelph) and a flow microcalorimeter (at Sherbrooke), mere used In this study. O u r results \{ere inconsistent with an ideal niononierdinier model, bvhich had been used in previous calorimetric studies o n this and other similar systems. O u r results mere consistent M ith an ideal monomer-dimer-trinier model, for which me obtained: K2 = 625 i 100 L mol, K 3 2 lo4 L2nio12 for the dimerization and trimeriration constants respectively, and AH,' = - 8.52 0.50 ltcal mol, AH,' = - 13.48 p 2 kcal mol for the molar enthalpies of dimerization a n d trimerization, respectively.

TRICHLR KRISHNAX, WAYNE CARL TO^ D U E R SAUL , GOLDMAN JEAK-LUC et FORTIER. Can. J . Chem. 57. 530 (1979). O n a applique une methode de dilution calorinietrique a u systeme acide benzoYquebenzene a 25'C. Deux calorimetres differents - un calorirnetre a masse (a Guelph) ct un microcalorimetre ecoulernent (a Sherbrooke) ont ete utilises dans cctte etude. Nos resultats ne avait ete utilise dans des etudes concordent pas avec un modele ideal monomere-dirnere q ~ i i calorimetriques anterieures sur ce systeme et d'autres semblables. Nos resultats sont en accord avec Lin modele ideal monomere diniere-triniere pour lequel on a obtenu des valeurs respectives de K2 = 625 i 100 L mol, K , = lo4 L2'mo12 pour les constantes de dimerisation et de 0.50 kcal mol, AH,O = - 13.48 trimerisation et des valeurs respectives de AH," = -8.52 i 2 kca1,mol pour les enthalpies molaires de dimerisation et de trimerisation. [Traduit par le journal]
-

Recently, a number of papers have appeared which describe a calorimetric dilution technique that enables one to determine the thernlodynarnic quantities AGO, A H 0 (and AS0) for self-association reactions that result from intermolecular hydrogen bonding (1-5). This technique is attractive because it is applicable to a wide variety of systems (5), and because it gives results rapidly. The method does, how-ever, require the assunlption that the heat evolved is due only to the change in the number of ideal molecular aggregates. When applied to carboxylic acids a n ideal monomer-dimes model \vas invariably assumed (2, 3, 5). Two fairly recent studies, however, cast doubt upon the validity of this model. In one (6) infrared data on the acetic acid - carbon tetrachloride system were investigated by the method of factor analysis. It was found that in all but the most dilute solutions species larger than dimers were present in appreciable concentrations. I n a second article (7) it was found

that monomers, dimers, and trimers mere required to of account for osmornetric data on benzene solut~ons long-chained carboxylic acids. In view of these articles and the only fair agreement between the calorimetric results and those frorn others techniques for the benzoic acid in benzene system ( 5 , 8-11), we considered it \vorthwhile to re-examine the calorimetric results. I11 the present work we used the results obtained from the heat of dilutionvalues measured in two different laboratories. A batch calorimeter in Guelph and a Picker flou ~llicrocalorimeterin Sherbrooke mere used.
Experimental
The benzene (Fisher, B-245 reagent grade) was purified and dried as described elsewhere (I2), a n d stored over molecular sieves (Fisher, 4 A). Traces of absorbed n~oisture the benzoic in acid (Analar, analytical reagent grade 9 9 . 9 2 assay) were removed by fusing in a platinum crucible at 135 5 5'C. Tmo separate analyses o n the final product by the sodium carbonate - sodium hydroxide mcthod (13, 14) rcsi~ltedin assay values of 99.97 and 100.COY,. A: the University of Guelph, the heats of dilution (A&,,)

0008-4042/79/050530-0XS0 i .00/0 1979 National Re\eal-ch Council of Can;ii!a/Conseil national d e recherche\ du Canadr!

were measured with a batch calorin~eter,built by Dr. W. C. Duer, which is similar to one described in ref. 15. With this instrument, fragile glass ampoules (capacity of 5 mL) fitted with capillary side-arms (designed to minimize solvent evaporation) were used for sample introduction. The heat of bulb breaking was found to be negligible. In all the experiments at Guelph the calorimeter vessel (volume of 200 mL) initially contained pure benzene and the a m p o ~ ~ l e s contained a known weight of a benzoic acid - benzene stock solution. Different final concentrations of benzoic acid in benzene were achieved both by using different concentrations for the stock solutions, and by varying the quantity of stock solution in the ampoule. The heats of dilution measured at the Universite de Sherbrooke were obtained with the con~inercial version (Sodev Inc.) of the Picker flow microcalorimeter. The principle of this calorimeter is described in detail else~vhere (16, 17). The measurements were done at a dilution ratio C,!Cf -. 2, where Ci and Cf are, respectively, the initial and final stoichiometric concentrations of benzoic acid in moliL. Due to the strong concentration dependence of the relative apparent molar enthalpy $ in the low concentration region (Fig. 1) we , measured most of the AH,,, on the flow system with C, 5 0.1 M. The high sensitivity (1 x ^ C )of the flow microcalorimeter allows such measurements with good precision, i.e., 0.5% or better. The solutions were prepared by weight. Molality-molarity interconversions were made using solution densities, which were measured with a flow densinieter (18). The excess volunle of mixing was found to be negligible. The effect of the water content of the samples on the dilution data was checked and found to be appreciable, as already observed by Flitt and Jaycock and others (1, 19-21). Therefore special care was taken in both laboratories to minimize water contamination. This precaution was especially important in the flow experiments where the low concentration region was probed. The water content of all samples run on the flow system were therefore titrated before and after the dilution using an aquatest Karl Fischer titrimeter (Photovolt, model values for samples with less than 702). We kept only the AHdi, 25 pprn water, for reasons which are now explained. A number of preliminary trial experiments were run with the flow calorimeter, in which lvater was deliberately added either to the solution, or to the solvent, or to both. Two concentrations of benzoic acid were used in these trials: 0.04 171 and 0.40 m. With 450 ppnl water in the solution, A$, was found to increase (i.e. become more negative) kith respect to the anhydrous situation by about 15%, for both the 0.04 171 and the 0.40 177 benzoic acid solutions. When 450 ppni water were present in both the solvent and the solution A+, decreased by about 5% with the 0.04 177 solutioll and it decreased by about 15% with the 0.40 ti1 solution. In another experiment, where 120 pprn water were added to the 0.04 w-r solution, A$, increased by about 2%. In still another set of preliminary experiments, two solutions of wet benzene containing 450 pprn and 120 pprn water (but n o benzoic acid) were diluted with anhydrous benzene. The A$, values ohserved in these trials were negligible with respect to our experiniental uncertainty. These last experiments demonstrate that the effect of water on A$, is due to changes in the extent of hydration of benzoic acid, rather than to the heat of dilution of water in benzene. These observations made it imperative to reduce the water content of these solutions as far as possible. It was found, in practice, that by taking sufficient precautions it was possible in almost every run to reduce the total water content of our systems to 25 pprn or less. The water content of the solutions did not change significantly (the experimental uncertainty in

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01

02

03

C4

05

MOLARITY

FIG. 1. Relative apparent molar enthalpy of benzoic acid in benzene at 25-C: solid line, this work; dashed line, calculated from K, and AH,' of Woolley and Zaugg (5). the mater analyses was 10 ppm) in the course of a dilution experiment. We found that when the water content of the solutions was within the range 0 to 25 ppm, the experimental A+,'s obtained from one run to the next were well within 0.50% of each other, which is our experimental uncertainty in A$,. Consequently we retained only those data obtained with the flow system where the water content was 0 to 25 pprn. The order of magnitude calculation given below provides a theoretical justification for the view that we can neglect the effect of water on our results provided the ~vater content of our solutions is less than 25 ppm. A previous study (which assunled a n~onomer-dimer model for the system benzoic acid in benzene) provides the following estimates for the hydration constants of benzoic acid in benzene at 25 C : K l l = 12.4 L/mol; K I Z = 248 L2/lnolZ,Kzl = 582 L2/n~o12 where K , ,,K,,, and K2, represent the hydration constants for the formation of the monorner-117onohydrate, the monomer-dihydrate, and thc dimer-monohydrate, respectively (22). In order to obtain an upper bound on the fractions of the benzoic acid species that were hydrated in our experiments with the flow calorimeter, we assume that all of the 25 pprn (1.21 x 10-3 M) was in the form of free (i.e. nonbonded) water. Thus the maximum fraction of the benzoic acid monomer that can be hydrated in our solutions at 25-C is given by:

F=

Concentration of hydrated monomer Total inonomer conceiltration

CAY J

C H t M VOL 57. 1979

TABLE E ~ p e r ~ m e n theat of dilution data at 25.0 i 0 1 C using the batch solution calorimeter 1 al

Run 1
171,~ 1 ? 7 ~X ~

Run 2
-

(molal)

loZ (molal)

AHdtlh (cal mol)

177,"

/?I,"

(molal)

lo2 (molal)
X

AH,,,h (cal mol)

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--

" n ? , ,1711 = stoich~ometric rnolality of benroic acid in benzene in the ampoule, and in the calorimeter (after the ampoule is broken), respecti\el) b A H d , ,is the heat of d~lution.

TABLE Experimental heat of dilution data at 25.0 & O.lcC using the Picker flow micro2. calorimeter Run 1
Cia (molar)
Cra

Run 2
-

(molar) 0.000813 0.002043 0.002845 0.004923 0.009312 0.02863 0.03629 0.04258 0.06390 0.09452 0.1337 0.1650 0.2406

AHoilh (cal mol)

510.5 456.8 449.3 363.3 289.8 187.3 169.8 162.0 133.3 113.4 98.53 91.48 79.87

Cia (molar)

Cf(' (molar)

AHdi," (cal 'mol)

493.6 492.8 449.8 435.7 385.5 290.0 235.9 229.3 147.4 107.6 102.0 84.39

0.001627 0.004097 0.005684 0.009890 0 . 0 1 870 0.05695 0.07216 0.08472 0.12705 0.1880 0.2660 0.3276 0.4778

0.003734 0.003734 0.004667 0.005665 0.008911 0.02066 0.03685 0.03685 0.10577 0.2632 0.2632 0.4430

0.001867 0.001867 0.002335 0.002834 0.004462 0.01036 0.01811 0.01843 0.05288 0.1299 0.1314 0.2218

"C, and C , are the iliiual and final concentrations bAHd,l the heat of dilution. is

Similarly the rnaxivllurn fraction of dilner that can be hydrated in our experiments is found to be 0.001 1. Thus by keeping the water content of the benzene solutions to 25 ppnl or less we keep the extent of hydration very small indeed.

Results and Treatment of the Data A total of 32 separate heat of dilution experimellts were carried out in two runs with the batch calorimAll eter and 25 with the flow microcalorii~~eter. the 0.l0C. The raw measurements were done at 25.0

data from both sets of experiments are entered 111 Tables 1 and 2 It is collventional to report heat of dllutlon data 111 terms of 4,. After several trlal calculat~ons, found \+e meter d ~ d that the data obtained n l t h the batch c a l o ~ not extend suffic~entlyinto the d ~ l u t e concentratloii reglon (Flg 1) to make such a reformulat~oneither meaningful or useful Howeber, the data from the d flow calorlineter d ~ extend to low enough concentrations to make t h ~ s re-formulation northuhlle. Therefore, the data In Table 2 \+ere treated by a procedure. slmllar large-scale graphical lnterpolat~o~l to one that had been used previously in the Sher-

TABLE Relative apparent molar enthalpy (- rjbL) of benzoic 3. acid in benzene at 25 C from a graphical interpolation procedure

In this section we describe two methods that were applied to our data. For the diinerization equilibrium
2M F? D

M (molar)

- $L

(cal mol)
1673 2161 2426 2567 2663 2945 3083 3166 3227 3272 3308

M (molar)

wherein the inonomers and diiners are each assumed to be ideal (see ref. 1 and belo\+): Ill K2 = [Dll[MI2 [Cl = [MI + 2[Dl [2I where [C] is the stoichiometric concentration of the solute and [MI and [Dl are the monomer and dimer concentrations. respectively (mol/L). Combi~iing eqs. [ I ] and [2], one gets

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brooke laboratory. The smoothed $ values so ob, tained are entered in Table 3. While a direct comparison of data i11 Tables 1 and 2 is not possible (because of the different concentration ranges involved and the difficulty of gettinr 4,'s from the data in Table 1) a n indirect colliparison (see text below and Table 4) indicated that the data from the two laboratories were consistent. The principal source of error in the evaluation of 4, stems from the required extrapolation to ~nfinite dilution. While a large number of experime~lts the on flow system were run with C , < 0.1 M in a n attempt to minimize this uncertainty, a substantial residual error in the extrapolation reinained. We estimate that the extrapolation led to an uncertainty of about +250 cal/mol in the absolute values of +,. The uncertainty i11 the values of A$, was of course much C less. We estimate that for 8 x l o p 4 M I 0.5 /If, the values of A$, are correct to f0 . 5 7 or better. ;Monomer-Dirrzer Model Several methods can be used to obtain values for K2 (the di~nerization coiista~lt) and AH,' (the enthalpy of dimerization) from heat of dilution data (1-3).

Method I can be related to the enthalpy of dimerization by the following equation

4,

[41

[C14,

AH,'[DI

Using eqs. [ l ] and [2].eq. [4] call be rearranged to give equation :

Thus a graph of 4, vs (-+,/[C])' leads to the evaluat~on AH,' and K, from the ~ntercept of and the slope of the best h e a r fit In fact, the plot of our results a c c o r d ~ ~ ito t h ~ se q u a t ~ o n shons a sllght g curve a ~ t values for C < 0 1 1 as call be seen froin h M Fig 2 We w ~ l lretulli to this point later. A Ilnear least-squares fit gave K, = 400 L'mol and AN,' = -7 6 kcal/mol Method 2 It was found by experience that the values of AH,' and K, that mere o b t a ~ n e d method 1 \$ere strongly by mere dependent 011 the absolute values of 4, \ $ h ~ c h used with eq [5] As explained previously, the absolute values of 4, were subject to cons~derable

+,

TABLE K z and AHzOfor benzo~c 4. acid In benzene at 25'C calculated on the basis of an ideal monomer-d~mer model Method of data treatmenta Method 2 Method 2 Method 1 Method 1

Data source This work, Table 1 This work, Table 2 This work, Table 2 Reference 5

K , ( L niol)
458 500 400 400 i 1OOh

- AHzO(kcallmol dimer)

7.7 8.4 7.6 7.3i0.Sh

P'LMethod1' and 'method 2' are described In text. bThese standard deviar~ons\\ere obtained from Professor Earl Woolley in a private communication.

534

C A N . J . CHEM.

FIG.2. Relative apparent molal enthalpy of benzoic acid in benzene at 25'C displayed as suggested by eq. [ 5 ] (rnonomerdimer model, n = 2) and eq. [7] (monomer-trimer model, 12 = 3).

uncertainty drle to the uncertainty in the extrapolation to infinite dilution. Therefore, it n.as desirable to treat our data by a second method. This method \vas applied t o the data from both the batch and the flow calorirneters. This method is a n iterative procedure that call be sulnrnarized as follons: first a n initial value for K , is chosen, and eq. [3] is used to calculate the change in of the ~ i u ~ n b e r mole of dimers All, = 11, - ui for each dilution experiment (the subscripts i and f refer t o the initial and final states). Then the enthalpy of dimerization. AH,', is computed by means of

where [Dl means d i ~ n e r concentration, V means volume, and q is the value of the measured heat change in the calorimeter. The calculatiori is carried out for all the experimental values and subsequently an average and a standard deviation is obtained for AH,'. These calculations are repeated for a nurnber of values of K2. The 'best' values of K2 and AH,' were obtained from that pair of values for which tlie standard deviation of AN,' was a minimum. When this procedure was applied to the data in Table 1 we

obtained: K2 = 458 Limol: AH,' = -7.7 kcal/mol dimer. When applied to the data in Table 2 we found K2 = 500 L,imol; AH,' = -8.4 kcal/mol dimer. The values of K , and AH,' from both methods are grouped together in Table 4, together with the values for these quantities reported previously by Woolley and Zaugg ( 5 ) . These authors used the I$, method on their calorin~etricdata which were obtained by a titrimetric procedure. Several points are immediately apparent from the entries in Table 4. First the data obtained by the batch and tlie flow calorimeters in this work are rnutually consistent, and they are both coilsistent with Woolley and Zaugg's data. Also, the uncertainties in this and in Woolley and Zaugg's work are of cornparable magnitude. Thus the A+,'s obtained here and in Woolley's work are consistent. The discrepancy in the ~ b s o l u f I$, values (apparent from e Fig. 1) obtained in this and in Woolley's work is a consequence of the fact that accurate absolute values require very accurate data in the dilute solution regime. The titrimetric procedure used by Wooliey and his collaborators inadequately probes region. this dilute solutio~l Of course, co~lsistencyof the above results really aniou~ltsto little more than a data check and cerdoes not prove the validity of tainly this consiste~icy mononier-dimer model. Indeed we are prompted for several reasons to be suspicious of this model. First, other authors using methods as diverse as infrared spectroscopy (6) and osrnometry (7) found that larger species in addition to dimers were required to account for their data on carboxylic acids in n o ~ ~ a q u e o u s solvents. Second, the values listed ~ I ITable 4 for K2 are s o m e ~ h a tlower than what is expected from previous studies invoi\.ing other experimental techniques. This discrepancy is demonstrated by the point with the symbol TJ in Fig. 3. We believe that the titri~netric calorinletric method employed by Woolley et 01. gives more weight to the high concentration regime than d o other experimental methods, so that the K, values extracted from the titrimetric data are too low. Third, we were bothered by the slight vs. curvature, which we believe to be real, in the (-+L/i[C])l plot (Fig. 2: upper graph). This curvature is apparent when a large scale graph is used. The scaling down and distortion that occurs on photographic reproduction makes this curvature unobservable in the upper graph of Fig. 2. We reasoned were present in that if aggregates larger than di~ners our solutions, then the use of a monomer-diiner model should result in a concentration-dependent K,. T o test this idea me evaluated K , and AH,' from A H d i , by applying method 2 to different concentration ranges. We split up our data from the batch

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+,

+,

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FIG.4. The dimerization equilibrium constant (K,) as a function of concentration.

and K, the trimerization constant. We applied eq. [ 7 ] to the data in Table 3 ; the results are plotted as the FIG.3. Various values of K2 (molar) for benzoic acid in benzene using the ideal monomer-dinler model: A, infrared lower curve in Fig. 2. As is seen from Fig. 2, a very that this (8); a, isopiestic method (9); 0, ebullioscopy (10); 0, obvious curvature results. It was co~lcluded cryoscopy (11); V , heat of dilution (5); x , heat of dilution model was clearly inconsistent mith our data, and it (this work with trimers included in the data treatment); solid was pursued n o further.
line is linear least-squares line through all the values.

calorimeter (Table I ) into two sets. In the first, the final solution collcentration (i.e. the concentration of the solution in the calorimeter after the ampoule is broken) was always less than some selected value and in the second it was always greater than this value. The of a number of such calculations clearly showed that K?. dropped wit11 increasing concentration. This concentration-dependence of K , is even more obvious with the data from the flow calorimeter (Table 2, since there the were measured \vith solutions covering a wide range of initial concentrations, i.e., 0.016 < c < 0.48 M. In Fig. 4, we i plotted the of for each (Table 2, eqs. [61 and [31, assumi~lgAH2 = - 8525 cal/mol dimer (our 'best' value, details given and setting the = (Cf + Ci)/2. It is clear from Fig. 4 that when the ideal monomer-dimer is applied to our data, the values of K, that result are strongly concentration-dependent. In view of these results, \ve considered it worthwhile to pursue other models, in an attempt to better account for our data. Monomer-Trimer Model This is an obvious alternative to the monomerdilner model. Using the same approach as was taken in the monomer-dirner case (method 1) one can show that for the case of an ideal monomer-trimer equilibriulll (1) :

AFil

Monomer-Dirner-Tri171er Model we next decided to fit our data to an ideal monomer-dimerptrimer model, hi^ model is the simplest logical extellsion of the ideal dilner and, as previously mentioned, it has been used to account for oslnometric data on solutions of long-chained carboxy]ic acids in benzene ( 7 ) . Of course ill taking this approach we assume that the deviations we observed from the ideal monomerdimer model are not due to non-ideality the monomers and din1ei-s themselves. While this is an unprovab~eassumption at present, it is consistellt with lnuch previous ky0i-k in this area (e.g. see ref. 1 and references contained therein) and it is partially supported by the evidence that molecules that are geometrically similar to bellroic acid but do not have a carboxylic acid group (e.g. chlorobe~lzene)are very nearly ideal up to of 1 M in llonaqueous solvents (1, 23). ~h~ approach described below is silnilar to one that has been previously described (4). F,, the case where trilners are assumed to comexist in equilibriunl with monomers and dimers, the relevant equations (assuming all the species behave ideally) are:

[g 1
191 [lo]

[7]

+,

AH
=

'
-

+ ~ K , [ M ] ' + 3K3[MI3 q = An,AH,' + AnTA~,' [C]+, = A f f 2 0 [ D ]+ AH3'[T]

[ C ] = [MI
3M F? T

where the trirnerization constant K , and the enthalpy of trimerization AN,', refer to the process :

where AN,'

is the molar enthalpy of trimerization

C A N J . CHEM. VOL 57. 1979

TABLE Values of the dimerization constant (K,), enthalpy of dimerization 5. (AHZo), trimerization constant (K,), and enthalpy of trimerization (AH,') of benzoic acid in benzene at 25'C from heat of dilution measurements
Value Parameter K, (L mol) AH,O (cal, mol d ~ m e r ) K, (L2,mo12) AH?' (cal mol trlmer) Flow calorimeter 625" 525" 9 000" - 13 475+ 100
-8

Batch calorimeter
--

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12 9 7 5 ~ 4 3 5 ~

5 e e text for d ~ s c u s s i o ~ i the ~ ~ n c e r t a ~ ~ i t i these quantities. of in e s TCa~culatedusing K 2 = 625, AH20 = 8 5 2 5 . and K , = 9000.

I11 eq. [9], An, is the change in the number of moles in of t r ~ m e r s a dilution experiment. T o obtain unique values for the four constants K,, K,, AH,', and AH,' , the we proceeded in two steps. F ~ r s twe d ~ v ~ d e d data C, in Table 2 Into two sets, one * ~ t h < 0.1 M and the other with C, > 0.1 IM. Then we used a n iterative procedure as follons For the set C, < 0.1 M u e assume only monomers and dimers are present to get a first estimate of K, and AH,'. Then these valucs of K,, AH,' are used in the C i > 0.1 M set to calculate a first estimate for K, and AH,'. These last values are now used to get ail improved pair of values of K,, AH,', from the dilute range. The entire procedure is repeated until the values obtained for the four constants stabilize. As a final step, all the data in Table 2 are combined into one set and the iterative calculation is repeated, starting with the last values of the four constants, until the standard dcviation (sd) for all the 25 points is minimum, where

The uncertainties in the values K , and AH,' given in Table 5 are probably close to those that are deduced from thc entries in Table 4 (i.e, sd K, 100; sd AH,' 0.5 kcalimol dimer). It is much more difficult to assess, even roughly, the net uncertainties in K, and AH,'. (The values of & 100 and k 4 3 5 cal given in Table 5 for AH,' are conditional uncertainties in that they depend on K,, AH,', and K, being perfectly correct.) This is because there is no concentration region in which trirners are the clearly predomil~ant species. From unpublished trial calculations, however, we feel that AH,' is probably correct to within 2 kcal, and that K , is of the right order of magnitude. Discussion

Our values of K, and AH,' calculated from the monomer-dimer-trimer model are in good agreement \bit11 those obtained from other ~ o r (Fig. 3). k The slope (d log K,,'d(l;'T)) through all the points leads to AH,' = -8.0 kcal/mol dirner compared with - 8.5 in the present m ork. Also our value for K, (625 Limol) falls almost perfectly on the leastsquares line. It renlains to account for the quasi-linearity of our The values we thus obtained for the four constants plot (Fig. 2, upper graph). T o get are grouped in Table 5. Since it is not possible to 4, vs. ( - +LjC)112 obtain unique Jlalues for the four constants K,, K,, better insight into this type of plot, we evaluated 4, AH,', AH,' using the data frorn Table 1 alone, the and (-$,/C)ll' using eq. [lo] for different values of stock solutions used being too concentrated, we K,, keeping K,, AH,', and AH,' fixed a t the values in utilized these newly obtained results (K, = 625 Table 5. The results of these trial calculations showed vs. (-+L/C)'/2 plot is a poor L/mol, AH,' = - 8525 ca1,'mol dimer, K, = 9000 that linearity of a ~ ~ 1 m o to ~calculate a value for AH,' using the criterion for the validity of the monomer-dimer I ) batch calorimeter data. The value thus obtained for model. For example: using K, = 90 000 (i.e., 10 AH,' is also entered in Table 5. As is seen from times our estimated value) which leads t o a n imTable 5, both values of AH,' agree to within their portant relative contribution of trirners to the stoichiometric concentration (for C = 0.10, the estimated standard deviations. The entries in Table 5 provide a good fit to the data fraction of acid in monomer: dimer : trimer form be in Tables 1 to 3 in that the calculated values of AHdil ~vould 0.06 : 0.42 : 0.52), the 4, vs. (- +L/C)1.'2plot were found not to deviate in any systematic (i.e. manifests only a slight curvature, which may, concentration-dependent) way from the correspond- depending on the quality of the data, be considered ing experimental values. In other words these values almost negligible relative to experimental error. Our value of AH,' per mol (AH30/3 = -4.49 provide a good fit to sets of A+, values that can be kcal/mol) is slightly more negative than AH,' per values in Table 3. constructed from the

+,

+,

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FIG. F(Ar)is the fraction of the stoichionietric benzoic acid concentration present as monomers, F ( 1 ) ; diniers, F(2); 5. a n d trimers, F(3). Curves obtained by eq. [8] with K , = 625 L,'mol a n d K , = 9000 L Z I m o l 2 .

mol (AH201'2 -4.26 kcal,!mol). This trend in = enthalpies has been noted for carboxylic acids in the gas phase (24), for lo11.g-chained carboxylic acid in benzene (7) and from quantum mechanical calculations (25). Also, our relative values of K , to K , are such that trimers make a significant contribution to the stoichiometric concentration for concentrations beyond 0.01 M. This is illustrated i l l Fig. 5, and is in line with what has been found for long-chained carboxylic acids in benzene (7) and for acetic acid in carbon tetrachloride (6). W e conclude, that except for very dilute solutions (i.e., less than M), the ideal monomer-dimer model is of questionable value in the study of carboxylic acid self-association. F o r this reason, we believe that studies of H-bonding or self-association by the calorimetric dilution method have to be done in such a way that the dilute concentration region is well characteri7ed, and this requires a highly sensitive microcalorimeter.

3. E. M . WOO1 L E Y tinil D. S . RUSH FOR^^ ki. Can. J . Chern. 52.

Acknowledgements We are grateful to the National Research Council of Canada and Le MinistGre de ]'Education d u QuCbec for financial support, to D r . C. Jolicoeur who tnade possible this collaboration between the two laboratories, and t o M. A. Simard for his technical assistance. We would also like t o thank Dr. Loren ~~~l~~ for his helpful suggestions concerlling the data treatment.
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