for a nitrate effect. Weak nitrate complexes have been suggested at low Mo(V1) concentrations (8). Rate Constants.

The constant k l was evaluated from a least squares analysis of the data under the conditions shown in Table I where Equation 5 holds. The ratio k2/k--1 likewas wise calculated under the conditions shown in Table I1 where Equation 6 holds. It was not possible to calculate k2 and k-l independently because the concentration of the intermediate was not known. The use of relaxation techniques to evaluate the faster steps could yield additional information. Average values of 22.03 0.42 1-mole-l-sec-l were obfor tained for k l and 15.38 + 1.09 m0le~-1-~ k 2 / k L Using these values for the rate constants, the reaction rates were calculated from the derived rate law [Equation 41 and compared with the experimental values. The results are shown in Figures 1-3, where the solid lines represent the rates calculated from Equation 4 and the rate constants, and the plotted points represent experimental values. The experimental points show an average deviation of about 5 % from the calculated curves.

CONCLUSIONS

12-MPA obtained ( I ) but also the rate of its formation. Thus, sample acidity must be carefully controlled, and the reaction progress monitored t o ensure that equilibrium has been reached. For those methods utilizing extraction of 12-MPA into organic solvents (9-12) or reduction of 12-MPA t o phosphomolybdenum blue, these problems are avoided because of the shift of the equilibrium. In addition, the kinetic data show a complex dependence on the Mo(V1) concentration and suggest the possibility of a competing reaction at high phosphate concentrations. Users of 12-MPA procedures should be aware of these complications. Based on the above studies, a new procedure for phosphate utilizing rapid initial reaction-rate measurements in the millisecond range has been developed. This new method can avoid complications due t o unfavorable equilibria and interferences. In addition, automatic phosphate determinations in the ppm range can be made accurately in less than 1 second so that the procedure is excellent for routine and continuous analyses. Details of this new procedure will be presented in a subsequent paper. RECEIVED review May 13, 1968. Accepted August 6, for 1968.
(9) D. F. Boltz and M. G. Mellon, ANAL. CHEM., 749 (1948). 20, (10) T. Hurford and D. F. Boltz, ibid., 40, 379 (1968). (11) C. H. Lueck and D. F. Boltz, ibid., 30, 183 (1958). (12) W. Kirsten, Microc/zimJ., 12, 307 (1967).

The results presented here have several important consequences for analytical chemists utilizing 12-MPA procedures for phosphate determinations. The efFect of acid on the reaction is complex, influencing not only the amount of
(8) S. P. Vorob'ev, I. P. Davydov, and I. V. S h i h , Zh. Neorg. Kliim., 12 (S), 2142 (1967).

Mechanism and Kinetics of Ion Pair Extraction. Rate of Extraction of Dextromethorphanium Ion
Takeru Higuchil and Arthur F. Michaelis Department of Pharmacrwtical Analytical Chemistry, Uniaersity of Kansas, Lawrence, Kan., and School of Pharmacy, Unirjersity of Wisconsin, Madison, Wis.
Relationships have been derived showing the dependence of the rates of extraction of ionic species from aqueous to organic phases as ion pairs. If the ratedetermining step or steps in the transfer process are assumed to be of intraphase diffusional nature, the classical Whitman two-film theory leads to an equation relating the flux from one layer to the other in terms of concentrations of the cation and anion, diffusivities of the cation and anion in the aqueous phase and that of the ion pair in the organic phase, and the effective thickness of the two diffusion layers. Experimental observations on a dextromethorphanium system were in agreement with the prediction of the theory.

ALTHOUGH TENDENCIES of many cations and anions to be THE extractable as ion-pairs into organic solvents have seen wide usage for separation and analytical purposes, relatively little attention has been paid to the nature of the basic process or processes which determines the rate of extractive transfer of the species involved. from aqueous t o organic phases or vice versa. We ( I , 2 ) among others (3-7) have reported earlier on the equilibrium behavior of these liquid-liquid systems. The
1 Please address all correspondence related to this paper to Professor T. Higuchi, 314 Malott Hall, Department of Chemistry, The University of Kansas, Lawrence, Kan. 66044.

present communication is concerned with a theoretical analysis of the rate process and results of several experimental studies designed to test its predictions. Although our present concern has been largely directed toward the extractive behavior of a protonated amine, dextromethorphanium ion, from water into chloroformic organic phase, the conclusions developed are probably applicable t o other related systems. The particular drug cation was selected for study because its equilibrium behavior has been SO well characterized ( I ) . A tacit assumption appears to have been made by some investigators that the basic transfer mechanism responsible for extraction from the aqueous to the organic phase of these ionic solutes involved preliminary formation of ion pairs in the water phase followed by transport across the interface (7).
(1) T. Higuchi, A. Michaelis, T. Tan, and A. Hurwitz, ANAL. CHEM., 39, 974-9 (1967). (2) T. Higuchi and K. Kato, J. Pharm. Sei., 55, 1080-4 (1966). (3) C. W. Ballard, J. Isaacs, and D. G. W. Scott, J . Pharm. Pharmacol., 6, 971 (1954). (4) R. L. Hull and J. A. Biles, J. Pharm. Sci., 53, 869 (1963). ( 5 ) G. J. Divatia and J. A. Biles, 50, 916 (1961). (6) G. Schill, Acta Pharm. Suecia, 2, 13 (1965). CHEM., 1282 (1967). 39, (7) T. D. Doyle and J. Levine, ANAL.
VOL. 40, NO. 13, NOVEMBER 1968

1925

DIRECTION OF MASS TRANSFER

CASTIRRED ACUEqS

I I I
CM+

I '
I I
I

Coi M'A-

I I I -I obi D- LIOUID
N TERFACE

STIRRED ORGANIC

PHASE

DISTANCE
Figure 1. Idealized diagram of a model ion pair transfer system Schematic diagram of ion pair transfer from aqueous to organic phase, through diffusion layer AXa in the former and A X o in the latter In line with this, Freiser et al. have recently shown that for special cases where inorganic cations capable of forming inner coordination compounds are extracted as ion pairs, the rate limiting step may be the formation of the coordination compound in the aqueous phase (8). Other studies of this type of ion pair extraction have been reviewed by Zolotov (9) and all cases confirmed the findings of Freiser et al. Among systems bearing more directly on the behavior of organic cations, Davies has investigated the rate of extraction of several inorganic and quaternary ammonium cations from water t o nitrobenzene (10). It was suggested as a result of these measurements that the rate limiting step was the transport of the ionic solute across the interfacial barrier, the slow process being one of diffusion of water molecules away from the ions in a selective manner at the interface and resolvation by molecules of the organic solvent. Davies' mechanism may not be strictly applicable to this study since these systems were concerned with extraction under conditions whereby only a limited degree of ion pairing occurred even in the organic phase. It is evident that in these interphase transfer processes, the rate limiting step may depend on the degree of agitation produced at and near the phase boundary. If the effective diffusional layers are relatively thick and the intraphase transport rates are slow, the observed overall rate of solute movement from the aqueous to the organic may be independent of the rate of movement across the boundary itself even though the latter may be significantly slow. In the present communication, we have assumed that this was the case and that for the systems considered the extractive process was taken to be rate limited entirely by the diffusional steps.
THEORETICAL CONSIDERATIONS

from a n aqueous phase, across a phase boundary into a n organic layer. Several possibilities exist even if it is assumed that actual movement across the interface is not rate-determining. For the particular systems of present concern where the cation is a n organic ammonium species, we have in effect the overall forward reaction BHH*O+ AH~o- (BH+A-)orgsnio
+

kt

It is possible that this may occur essentially through the mechanism BHE~o+ AH,o-

e(BH+A-)E~oe (BH+A-)organic

fast

slow

the ion pair actually forming in the aqueous phase and subsequently diffusing across the boundary. An alternate possibility is that the diffusion of the components occur largely in their respective unionized form, BHH~o+ HzO

eB H ~+ H D + O
4

A-

Baiganic H20 e HAH,o OH-

H Aorganic
HAorganic

+ Barganio e (BH+A-)organio

There are a number of mechanisms which can account for the apparent net diffusional movement of ionic components
(8) B. E. McClellan and H. Freiser, ANAL.CHEM., 2262 (1964). 36, (9) Yu.A. Zolotov, Dokl. Akad. Nauk SSSR, 162, 577 (1965). (10) J. T. Davies, J. Phys. Coll. Chem., 54, 185 (1950).

If the transfer took place largely through this mechanism, it is evident that the rate will depend largely on the concentration only of the anion or only that of the cation and the diffusivity and the acid-base properties of these species. The rate should show a large dependence on pH. The simplest and, in our view, the most reasonable mechanism for the ion-pair transfer process can be developed on a modification of the classical Whitman's two film theory (11, 12). The usual two-film theory is concerned with dif(11) W. G. Whitman, Chem. Met. Eng., 29, 147 (1923). (12) K. F. GordonandT. K. Sherwood, A.Z.Ch.E.J., 1,129(1955).

1926

ANALYTICAL CHEMISTRY

fusional transport of a neutral solute across two hypothetical film layers in contact with each other at the interface, the ratedetermining step or steps being the diffusional movements in the immediate neighborhood of the interface and within the two contacting layers. The ion-pair process would be expected t o differ largely from this situation in that in the aqueous phase we are concerned with simultaneous transport of two species, cations and anions. Consider a model system as diagrammed in Figure 1 consisting of a stirred aqueous layer and a stirred organic layer with ions being extracted from the former t o the latter, ion pair formation occurring at the interfacial barrier. Following Whitman as confirmed by Gordon and Sherwood (12), assume that the solute species in the immediate interphasal zone are effectively in equilibrium across the interface and that the rate limiting steps involve diffusional movement effectively across a film thickness AX, in the aqueous layer and AXo in the lipoidal layer both directly adjacent to the interface. On this basis, the overall rate of passage of the ionic species in either direction can be readily derived. The following symbols are used :

and Pi = [C

- Cildc __ AXo
dp AX0

(4)

By substituting Equation 4 into Equation 2, we obtain

where

Solving for Ci we have 2Ca

=

-[Ada

- Cdc + W ]
dc

[(Ada

-2 +

0) +

4] % dc

(6)

K,,

= extraction constant as defined before

Pi -__ Arc,

Since it is evident that Ci must be positive, only the positive second term need be considered. An excellent approximation for C, can be obtained for cases where A is substantially greater than C or the converse. For C < A it can be readily < shown by binomial expansion that Equation 6 reduces to
Ct
=

C and Ci
A and A i

= concentration

of cation in bulk aqueous

Ada

wc - Cdc + w

(7)

phase and aqueous interface, respectively

= concentration of anion in bulk aqueous phase

Substituting this into Equation 1 we have:

and aqueous interface, respectively P and P ,

=

concentration of ion pair in bulk organic phase and organic interface, respectively Since Cdc is assumed to be much less than Ada this reduces to (9)

AX, and AXo = thickness of effective diffusional layer on aqueous and organic sides of interface, respectively d,, da, and d p = diffusivities of cation and anion in aqueous phase and of the ion pair in the organic phase, respectively It is evident on the basis of Ficks first law that the net diffusional flux per unit area Q (If diffusivity is expressed in terms of cm2 sec-l and the concentration gradient in moles/ liter/cm, Q represents the number of moles diffusing across a cross sectional opening of 1000 cm2 per second.) is identical at the interface for the cation and anion in the aqueous phase, and for the ion pair in the organic layer :
[C - Cildc - [ A - Ailda AXa AXa

Similarly, it is evident that for C >> A

Q=-

A Xu

Cdc

+ I
w

- [Pi - Pldp AXo

(1)

and

These equations should describe the rates of forward movement (from aqueous t o organic) if these processes are purely diffusionally controlled as we had assumed in their development. In systems where essentially all of the cation (or the anion) is initially as the ion pair in the organic phase, P cannot be taken to be zero and the diffusional movement will be in the opposite direction. For the reverse flowing system, it can be shown readily that for the case where the anion concentration in the aqueous layer is relatively large and the initial cation concentration in the aqueous layer is essentially zero, the flux of ion pair species from the organic phase would be

Substituting for A i into Equation 1 we have, considering only the second and third terms in Equation 1,

e=--

AXo (Ada

- Cdc + W>
If

PdP

[c- CtldC

= [A

- Pi/CiKe,]da

(2)

the negative sign indicating flow in the opposite direction. w > AdAthis reduces to >

And if we consider only the forward rate where P is effectively zero

[C

- Cildc - Pidp - _
AXa AX0

(3)

a completely logical relationship; the indicated rate determining step being in the organic phase.
VOL. 40, NO. 13, NOVEMBER 1968

1927

STIRRER SAMPLING TUBE U W R PHASE

WATER OUT

WATER ACKET

'

INERT R P S T l C COVERED MAGNETIC STIRRING BAR

J
LOWER STIRRER (MAGNET)
ri/

4:
I

8
2

Figure 2. Diagram of extraction cell used in determination of extraction rates ForAdA >> w

This suggests that for this system the rate determining step is the diffusional movement of the released cation from the interface into the aqueous phase.
EXPERIMENTAL

20

40

60

80

100

TIME (MIN.)
Figure 3. A typical experimentally observed rate plot for the extraction of dextromethorphan hydrobromide from aqueous to organic phases observed spectrophotometrically, T = 25 "C Concentrations: 5 X 10-4M dextromethorphan, 0.10M NaBr, 0.10M phosphate buffer. Organic phase = 100% CHCL,, stirring rate = 40 rpm Other than those designed to determine pH dependence all runs were carried out with the aqueous phase at pH = 3.00 with 0.10M phosphate buffer. No pH change was observed during or after any run. Potassium sulfate was added to maintain constant ionic strength. The experimental plots were prepared by plotting the logarithm of the absorbance of the infinity sample minus that of the sample as a function of time. Linear plots were obtained over the observed time interval and the observed rate constants were calculated from the slopes. It was necessary to correct the observed values for the reverse process when the latter became appreciable. The forward rate constant, k ) , was taken as the rate constant for the extraction from water to organic phases and the reverse rate constant k,, for the extraction from organic to aqueous phases. Since the distribution ratio, D , is equal to the ratio of the forward to the reverse extraction rate constant, k ) may be expressed as a function of the observed rate of constant and the distribution ratio : k , = ____ 1 1ID Similarly when the reverse extraction was observed :

With the exception of the procedures used for the determination of the rate of extraction, the experimental equipment, reagents, and procedures have been previously described ( I ) . Essentially all rate studies were carried out with dextromethorphan as the test substance. Procedure for Determination of Rate of Extraction. A schematic diagram of the extraction cell used in these experiments is shown in Figure 2. Each phase was smoothly stirred, separately and in opposite directions, using two DC driven universal motors which powered an overhead stirring bar and a lower magnetic stirring bar. The relative stirring rates were so adjusted as to provide an essentially quiescent interface. Incoming line voltage was passed through a large constant voltage transformer. Frequent determinations of the stirring speeds during the course of all runs showed them to be constant within =t2%. Temperature was maintained by circulating water from a constant temperature bath through the water jacket of the cell. Temperatures within the cell were held constant within 1 0 . 1 degree. The rates of solute transfer were determined in the following manner: aqueous buffer solutions and the organic phase were first mutually saturated with respect to each other and 100 ml of each were placed in the cell. While thermal equilibrium was being reached the stirring speeds of the motors were adjusted to a selected value, nearly all of the runs being carried out at 40 rpm. At the beginning of each run, a definite volume of a solution of the substance to be studied was added by syringe to the appropriate phase after withdrawal of an identical amount of that phase with another syringe. Samples of the other phase were withdrawn by syringe at time of intervals such that at least two half-lives were observed in most cases. At the same time an equal volume of the nonsampled phase was withdrawn in order to maintain a constant volume ratio between the two phases. Infinity values were obtained by withdrawing 5.0-ml samples of each phase after sampling was completed and shaking them in a separatory funnel while immersed in a water bath at the same temperature as the extraction cell until equilibrium was obtained.
1928
ANALYTICAL CHEMISTRY

kobs

It is evident that kf,for example, is related to Q,the diffusional flux per unit area by k ) = FQ/C where F is the geometric factor corresponding to the surface area volume ratio (approximately 0.2 cm-l in the present case) and C, the concentration of the extracted species in the aqueous phase.

STIRRING RATE ( R P M )
Figure 4. Effect of stirring rate on forward extraction rate constant for extraction of dextromethorphan from aqueous to organic phases, T = 25 "C Concentrations: 5 X 10-4M dextromethorphan, 0.01M NaBr, 0.10M phosphate buffer. Organic phase = 100% CHCL3
RESULTS AND DISCUSSIONS

0.50

1.00

Figure 5 Effect of bromide ion concentration on k, for . extraction of dextromethorphan hydrobromide from aqueous to organic phases, T = 25 "C, p =1.09 Concentrations: 5 X 10-4M dextromethorphan, 0.10M phosphate buffer, K2S04 to maintain ionic strength. Organic phase = 100% CHCL3. Stirring rate = 40 rpm against the bromide concentration in the aqueous phase, the data indicating relatively small dependence over 20-fold change in the concentration of the anion. In Table I are listed the observed rate constants for the extraction of dextromethorphan in presence of several anions along with their mobilities. It is evident that the several values of k f are approximately constant although the ionic mobilities vary by as much as 50%. These findings are in agreement with Equation 9. Since in these systems w < Ad,, the flux per unit area <

Rate of Extraction and Stirring Rate. Although the experimental setup employed in these studies was relatively unsophisticated, the equipment and the procedure employed gave remarkably consistent and readily reproducible data. Figure 3 shows a typical first order plot obtained from these kinetic measurements. In general the slopes of these lines, corresponding to kobs,were reproducible to roughly 5% for repetitive runs. Usually systems were so selected that the k , term in kobs = kf

+ k,

could be neglected. Where this could not be done, the forward rate constants were corrected by using distribution values. In Figure 4 is shown the observed dependence of k , on the stirring rate. These experimental observations were made using pure chloroform as the organic phase and an aqueous phase having the following concentrations: 5.0 x 10-4M dextromethorphan phosphate, 0.10Msodium bromide, and 0.10M phosphate buffer. The pH of the aqueous phase was 2.10 and the temperature 25.0 "C. Attempts to obtain values of k for stirring speeds greater than 50 RPM led to less reproducible results, the behavior probably being due to disturbances caused by vortex formation at these speeds. The rate constant was essentially independent of dextromethorto 5 X 10-4M. phan concentration from 1 X The linear and direct correlation of the extraction rate with stirring (which would be expected to be inversely related to the effective thicknesses of the diffusional film layers) provides a strong support for the film theory. It is evident that markedly higher rates of stirring which may reduce the effective thickness of the layer by one or two orders of magnitude may lead to interface controlled process but such conditions appear to be difficult to attain in practice. Dependence of Extraction Rate on Anion Concentration and Nature. Distribution ratios of dextromethorphan and other high molecular weight ammonium species between chloroform and water are highly dependent on the concentration and the nature of the anions present (1-7). The rate of forward extraction does not, however, appear to be influenced by these factors. In Figure 5 the experimentally observed forward rate constant for dextromethorphan is shown plotted

and kf =
Fdc
~

AX,

where F is the geometric factor. In the above relationship, only the concentration and diffusivity of the cation and the film thickness appear. Thus, the rate is predicted to be independent of the nature and concentration of the anion (when present in large excess). These observations render rather improbable any mechanisms based on preliminary formation of the ion pairs in the aqueous

Table I. Forward Extraction Rate Constants and Ionic Mobilities of Various Anions Paired with Dextromethorphaw Ionic mobility

x 1017b

k f X l o 2 (min-l) (cm/sec/dyne) Anion Bromide 1.08 12.7 1.12 42.4~ Trichloroacelate Perchlorate 1.12 68.8 Iodide 1.10 71.6 T = 25 " C ; organic phase = 100% chloroform. Concentrations: 5 X 10-4 dextromethorphan phosphate, 0.10.44 NaX (where X is the extractable anion), 0.10M phosphate buffer. Stirring rate = 40rpm. pH = 3.00 b B. E. Conway, "Electrochemical Data," Elsevier Publishing Co., Amsterdam, 1952, p 145. c Estimated from value for chloroacetate ion.
0

VOL. 40, NO. 13, NOVEMBER 1968

1929

':t8,0t
12.01
v

1.1

Ibr

1.0,

0.9-

,
I

- 0.82 0.7.E
0.6-

Q
X
w-

4.0L

0 0.4.
0.2,

0.5-

0.32.0
2.4 2.8

EXPERIMENTPL

3.2

36 .

PH
Figure 6. Effect of p H on extraction of dextromethorphan hydrobromide from aqueous to organic phases, T = 25 "Cy1.1 = 0.43 Concentrations: 5 X 10-4M dextromethorphan, 0.10M NaBr, 0.10M phosphate buffer, K&O4 to maintain constant ionic strength. Organic phase = 100 HCC13; stirring rate = 40 rpm

" 1
00

CALCULATED

2.0

4.0

6.0

8.0

10.0

12.0

14.0

CCHCI,]
Figure 7. Effect of chloroform concentration in carbon tetrachloride on k , for the extraction from aqueous to organic phases, T = 25 "C Concentrations : 5 X 10-4M dextromethorphan, 0.10M NaBr, 0.10M phosphate buffer. Stirring rate = 40 rmp. Calculated points are based on Equation 9

phase followed by their transfer t o the organic phase. Since the observed rate exhibits practically no dependence on bromide ion concentration even at its lowest level, it is rather unlikely for this particular system that the associated species plays a significant role in the transfer process. This is particularly so in view of the fact that the observed equilibrium distribution ratio was directly dependent on bromide over the entire concentration range studied. We recognize the possibility and probability that systems can occur in which high degrees of ionic association may occur in the aqueous phase (7). This may be particularly true for polyvalent ionic species. In such systems, however, we should see marked deviations from the equilibrium relationship defining K,,, the observed distribution ratio becoming insensitive to changes in the concentration of the major ionic compound. Dependence on pH. The inflilence of the pH of the aqueous phase on the observed rate of transfer of dextromethorphan from aqueous to the organic phase is shown in Figure 6. If the extractive process was mediated largely through the neutral form of dextromethorphan, the pH rate profile would have shown a significant dependence on hydrogen ion concentration. The experimental data definitely indicate that this is not the case. It is also evident that if the free base form of the drug was actually participating in the extractive process, the absolute forward rate would be substantially less than the rate of extraction of organic species which can not exist in any but the neutral state. Comparisons of the transfer rate of phenol and dextromethorphan hydrobromide into chloroform has shown that the two were essentially the same. Dependence of Rate on Kex. The relative influence of change in K,, on the rate of extraction into an organic phase composed of varying concentration of chloroform in carbon tetrachloride was investigated, again using dextromethorphan as the test ion. Since we have already determined ( I ) the influence of chloroform level on K,, and since the diffusivity and the thickness factors in

we can combine into a single constant which would not be expected to change significantly with the composition of the organic layer, or Constant w=K,, we can calculate the relative change in w with chloroform concentration. On this basis we can rewrite Equation 9

kI where

QF P c - - = a ( l - K ) T +

Since K,, values are known for dextromethorphan ( I ) , numerical values of and P can be obtained from two k , values determined at two values of Kex. In Figure 7 is shown the observed influence of chloroform concentration on k f . The smooth line and the circles represent the relationship predicted by Equation 9, the two constants being calculated from k , values observed for 2.46 and 12.4M chloroform concentrations. It is evident that the predicted relationship holds as well as one can expect.
(Y

CONCLUSIONS

It is apparent from the experimental results developed that the rate of extraction for the stirred two-layer system employed in these studies follows the relationships expected on the basis of the film theory. One can ask, however, how closely this situation may approximate the conditions which may exist in a separatory funnel, a countercurrent extractor or a liquidliquid partition chromatographic column. Some insight may be gained from the approximate AXu values indicated in the present studies. At 40 rpm according t o Table I, kl = 0.011 min-* or 2 X sec-'. Since for the particular cell used F = 0.2 cm-l
Fd, Axu = kl

0.2 X 5 x 2 x 10-4

= 0.005 cm

1930

ANALYTICAL CHEMISTRY

where the diffusivity value of dextromethorphanium ion was assumed to be of the order of 5 X cm2sec-I which is that of sucrose. The estimated film thickness in the aqueous layer of approximately 50 microns at the indicated stirring speed appears t o be quite reasonable. It would appear most likely that, on this basis, Equation 9 and similar relationships would be valid to film thickness down t o as low as 5 microns. Thus extractive rates from dispersions of droplets of aqueous phase in a n organic phase of the size of 1 t o 2 mm in diameter would

be expected to be diffusion controlled. Even for partition chromatographic column where the particulates holding the internal phase may be smaller, the general theory may very well still apply. RECEIVED review April 3, 1968. Accepted August 7, for 1968. This study was supported in part by grants from Warner-Lambert Pharmaceutical Company, Morristown, N. J., and Smith Kline and French Laboratories, Philadelphia, Pa.

Extraction of Nitric, Hydrochloric, and Perchloric Acids into Carbon Tetrachloride Solutions of Methylenebis[di-n-Hexylphosphine
Jerome W. OLaughlin, Deanna F. Jensen, Jerry W. Ferguson, John J. Richard, and Charles V. Banks
Institute,for Atomic Research and Department of Chemistry, Iowa State University, Ames, Iowa 50010 An attempt is made to treat the extraction of nitric, perchloric, and hydrochloric acids from aqueous solutions into carbon tetrachloride solutions of methylenebis[di-n-hexylphosphine oxide], MHDPO, in terms of relatively simple equilibrium expressions. Partition data suggest acidic species in the organic phase of the general stoichiometry n-MHDP0.xH20.yHA. In the case of nitric acid and 0.05M MHDPO the predominant species are those where n = 1, x = 0, and y = 1 or 2; K,(y = 1) = 4.88(M)-2 and = 2) = 0.18 (M)-2. There is also evidence for species where n = 2, x = 1, and y = 1. The latter species appears to be dominant in the case of perchloric acid where kHcIoI = 2.0 x 103(M)p for 0.05M MHDPO. Extensive aggregation was observed in the organic phase at high initial acid concentrations with third phases appearing in the cases of perchloric and hydrochloric acids.

METHYLENEBIS[DI-N-HEXYLPHOSPHINE OXIDE], MHDPO, and related compounds with the general formula,
(R)r-P-(CHJ,-P-(R)z

1
0

have been shown t o be powerful extractants for many metal salts ( I ) . These diphosphoryl compounds, like TBP and TOPO (tri-n-octylphosphine oxide), are usually diluted with some solvents (in the case of MHDPO, carbon tetrachloride, benzene, and 1,2-dichlorobenzene have been used) for liquidliquid extraction studies. Equilibration of a solution of one of these extractants with a n acidic aqueous solution of a metal salt results in the partition of the salt, the acid, and water between the two phases. In order t o treat the extraction of a metal salt in a quantitative manner it is necessary t o study the partition of water and the acid and t o determine the nature of the water and acid species existing in the organic phase. In principle, one might hope t o determine a series of equilibrium constants for the formation of the various species involved which would completely characterize the system. In practice, this is often not feasible, but some useful insights can be obtained from careful studies of relatively simple systems.
(1) J. W.

The partition of water into carbon tetrachloride solutions of MHDPO and some related compounds was recently reported ( 2 ) . In the present paper, the partition of the mineral acids into carbon tetrachloride solutions of MHDPO is reported and a n attempt is made t o treat the data in terms of simple equilibria involving the species believed t o be formed in the organic phase. The extraction of nitric, hydrochloric, and perchloric acids by 1,2-dichlorobenzene solutions of TOPO, MHDPO, and analogous diphosphoryl compounds (n = 2, 3, and 4) was previously reported (3); the data reported were for the extraction of these acids from relatively concentrated acid media, and n o attempt was made t o determine the nature of the acidic species in the organic phase or to calculate equilibrium constants. In a n earlier paper ( 4 ) the extraction of nitric acid by MHDPO in 1,2-dichlorobenzene was reported and a conditional equilibriumconstant of 15.2 was reported for the extraction of the species MHDPO . H N 0 3from 1Mnitric acid. While the present work was in progress, Goffart and Duyckaerts ( 5 ) reported on the extraction of nitric acid by benzene solutions of MHDPO and analogous diphosphoryl compounds where n = 4 or 5 . They interpreted their data in terms of the stepwise neutralization of the two phosphoryl groups with the formation of the species Y.HNOJ and Y . 203 in the organic phase, where Y stands for the extract= 0.35 i ant. They reported Z?, = 10.2 f 0.9 (M)-2 and 0.02 (M)-* for MHDPO. In the present investigation it was found that the latter approach was only of limited usefulness. Extensive aggregation was found in the organic phase in the case of perchloric and hydrochloric acids with third phases appearing when the initial acid concentration was over 1M or 5M, respectively. Third-phase formation was noted in the case of nitric acid only when 0.2M solutions of MHDPO were equilibrated with concentrated nitric acid (over 12714) but vapor pressure lowering

z,

(2) J. W. OLaughlin, J. J. Richard, J. W. Ferguson, and C. V. Banks, ANAL. CHEM., 40,146 (1968). (3) J. E. Mrochek and C. V. Banks, J. Inorg. Nucl. Chem., 27,

OLaughlin in Progress in Nuclear Energy, Series IX, Vol. 6, D. C. Stewart and H. A. Elion, Eds., Pergamon Press, London, 1966, Chapter 2.

589 (1965). (4) J. E. Mrochek, J. W. OLaughlin, H. Sakuri, and C. V. Banks, ibid., 25, 955 (1963). ( 5 ) J. Goffart and G. Duyckaerts, Anal. Chim Acta, 39, 57 (1967).
VOL. 40, NO. 13, NOVEMBER 1968

1931