An eigenvalue method for determination of multicomponent diffusion coefficients.

Application to NaOH NaCl HzO mixtures + +

DEREKG. LEAIST'A N D ROBERT A. NOULTY
Departrnerlr qf' Chemisrry, Urliver.si~of' Wesrerrl O n a r i o , Lor~rlorr.Otlt.. Carlacla N6A 5B7
Received June 25. 1984

DEREKG. LEAISTand ROBERTA. NOULTY.Can. J. Chem. 63, 476 (1985).

A general method for the determination of multicomponent diffusion coeff~cientsis developed using the algebraic technique
of matrix diagonalization. When linear combinations of measurements from several multicomponent diffusion experiments
performed with different initial concentration gradients (but with the same final composition) are analyzed as simple binary
data, particular combinations may be found that transform the multicomponent diffusion coefficient matrix D to diagonal form
and thus yield time-invariant. pseudo-binary diffusion coefficients: the eigenvalues of D. Since the matrix that diagonalizes
D is given by the coefficients used to form the linear combinations, D is easily recovered by the inverse transformation. The
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 84.78.191.92 on 04/09/11

advantages of the eigenvalue method are briefly discussed. For testing purposes, ternary diffusion coefficients are determined
from conductance measurements for d~luteaqueous NaOH + NaCl mixtures. Diffusion of NaOH in aqueous NaCl is
significantly more rapid than in pure water, and large coupled flows of NaCl are observed. The results are in close agreement
with behavior predicted by Onsager-Fuoss theory.

DEREKG. LEAISTet ROBERTA. NOULTY.Can. J. Chem. 63, 476 (1985).

Faisant appel i une technique algkbrique de diagonalisation des matrices, on a developpe une mCthode gkntrale permettant
de determiner les coefficients de diffusion i plusieurs composantes. Lorsqu'on analyse, sous forme de donnkes binaires
simples, des combinaisons linkaires de mesures provenant de plusieurs expCriences de diffusion i plusieurs composantes,
rkaliskes avec des gradients diffkrents de concentrations initiales (mais avec la meme composition finale), on peut trouver des
combinaisons particulikres qui permettent de transformer en une forme diagonale la matrice D du coefficient de diffusion i
plusieurs composantes; on peut ainsi obtenir des coefficients de diffusion peudo-binaires qui ne varient pas avec le temps.
Puisque la matrice qui diagonalise D est obtenue i partir des combinaisons utilisees pour former Ies combinaisons lineaires.
on peut facilement rtcupkrer D par la transformation inverse. On discute brikvement des avantages de la mCthode des valeurs
For personal use only.

de eigen. Pour fins de verification, on a determink les coefficients de diffusion ternaires i partir de mesures de conductivitt
sur des solutions aqueuses diluees de mClanges de NaOH + NaCI. La diffusion du NaOH dans le NaCl aqueux est beaucoup
plus rapide que dans I'eau pure et on observe d'importantes migrations couplCes de NaCI. Les rksultats obtenus sont en bon
accord avec le comportement prCdit par la thCorie de Onsager-Fuoss.
[Traduit par le journal]

I. Introduction tial conditions as simple binary diffusion data. Particular com-

Multicomponent diffusion is of theoretical interest and con-
siderable practical importance ( 1 , 2). In many cases the dif-
fusivity of a solute in a multicomponent mixture is significantly
different from its binary diffusivity, especially if the solutes are
electrolytes or they react chemically (3-8). Moreover, because
diffusional flows interact, multicornponent diffusion of a com-
ponent produces countercurrent or cocurrent flows of other
components in the mixture. If the interaction is strong, a gra-
dient in concentration of one component can effectively control
transport of a second component.
Multicomponent diffusion is measured by classical gradient
techniques (8- 16). Typically, a system is prepared with initial
concentration differences"across a sharp boundary. As the sys-
tem relaxes toward thermodynamic equilibrium, changes in a
concentration-dependent property (such as the refractive index)
are measured along the diffusion path. Diffusion coefficients
are then obtained by fitting mathematical solutions of the mul-
ticomponent diffusion equations to the measurements. Because
these solutions are complicated functions which contain the
diffusion coefficients as non-linear parameters, determination
of diffusivities for multicomponent systems by this procedure
is substantially more difficult than for binary systems (17).
The purpose of this work is to develop a simpler method for
the analysis of multicomponent diffusion data. Rather than fit
solutions of the diffusion equations to measurements from indi-
vidual experiments, we propose to treat linear combinations of
binations diagonalize (18, 19) the multicomponent diffusion
equations and yield time-invariant, pseudo-binary diffusion co-
efficients - the eigenvalues of the multicomponent diffusion
coefficient matrix D. The eigenvalues provide D in diagonal
form. We show that the coefficients used to form the linear
combinations define the matrix that diagonalizes D, and that D
is easily reconstructed by the inverse transformation using ma-
trix inversion and multiplication.
To evaluate the eigenvalue method, ternary diffusion coeffi-
cients have been determined for NaOH NaCl + H?O mix- +
tures. This system was chosen in order to test recent predictions
(21) that aqueous hydroxides diffuse much more rapidly in
supporting electrolytes than in pure water. Another purpose of
the study was to determine whether or not pH gradients pro-
duced by hydroxide gradients, like pH gradients produced by
acid gradients (6-8), can generate large coupled flows of salts.
Coupled transport driven by pH gradients has applications to
separation technology and plays vital roles in biological sys-
tems (22-24).
2. Theory
n + 1 comporzerzts
Provided the concentration gradients are not too large, iso-
thermal diffusion in a system containing n +
l components
may be described by rz coupled equations (25)
n

measurements from experiments performed with different ini- [I] ac,/at = C D;~V?C~ i = I , 2, . . . , n
P= l

' To whom all correspondence should be addressed. where c, is the concentration of component i in moles per unit
 LEAIST A N D NOULTY
volume, t is the time, and V' denotes the Laplacian operator.
Multicomponent diffusion coefficient D, measures the flux of
component i produced per unit concentration gradient in com-
ponent k. In matrix notation
where c denotes the column vector of n component concen-
trations and D is the n X n matrix of diffusion coefficients.
Consider linear combinations (18, 19) u; of the component
concentrations defined by
[3] ci= z AiPuP
n
P= l
Upon substitution of c = Au into eq. [2] and multiplying by
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A-', the diffusion equations may be rewritten as
[4] du/at = (A-'DA) V'u
If coefficients A, are chosen so that the columns of A are
eigenvectors of D, the transform of D is diagonal (20)
For personal use only.
and the transformed diffusion equations
are de-coupled. D; are eigenvalues of D and ui are solutions of
the binary diffusion equations.
Reduction to diagonal form is a powerful technique (18, 19)
that is frequently used to solve coupled differential equations.
Can the same technique be used to measure multicomponent
diffusion coefficients? Consider n diffusion experiments run at
the same final composition of the system but with different
initial concentration gradients. 'The idea is to use measurements
from these runs as a "basis set" of data from which suitable
linear combinations may be taken that diagonalize D and thus
simplify the analysis.
Let Y represent the refractive index (4-6, 8- 13), conduc-
tance ( 1 4 , 2 I), density (26), optical absorbance (27), or another
concentration-dependent property measured along the path of
diffusion during an experiment. For initial concentration differ-
ences Aci(0) across a sharp diffusion boundary, the corre-
sponding difference in Y is "
n initial conditions Xi may be constructed from
[7] AY(0) = 2 SiAci(0)
,= 1
where Si are derivatives
evaluated at the final composition of the system. Xi will be used
to denote the fraction of AY(0) contributed by component i.
n
[9] Xi = S,Ac,(O)/z SI;Ack(0)
I=I
Apparent binary diffusion coefficients D,(t) may be obtained
from multicomponent experiments by analyzing measured val-
ues of Y as if they were from a binary experiment (8, 1 1, 2 1,
28, 29). Apparent diffusion coefficients obtained in this man-
ner usually vary with time. For example, if an experiment is
477
performed with initial concentration gradients in solutes 1 and
2, and 1 diffuses rapidly compared to 2, values of D,,(t) will be
large initially but will decrease toward the end of the experi-
ment as the initial gradient in 1 decays rapidly and diffusion of
slower solute 2 predominates.
Although apparent diffusion coefficients are generally time-
dependent, consider an experiment with particular initial condi-
tions X,"' such that the column vector of initial concentration
differences Ac"" (0) is an eigenvector of D
Under these conditions
and hence
Consequently, the experiment behaves as a simple binary dif-
fusion experiment with time-invariant, pseudo-binary diffusion
coefficient equal to eigenvalue DL.Once values of Xi'" and Dk
are established, the multicomponent diffusion coefficients are
easily determined using
and the inverse transformation
Since D is unknown at the start of the experiments, it is of
course virtually impossible to choose the exact initial condi-
tions that diagonalize D. Nevertheless, by taking linear combi-
nations of data from experiments with different (specifically,
linearly independent values of Ac(0)) initial conditions, mea-
surements corresponding to arbitrary initial conditions may be
obtained. For instance, if AY;(t)/AY;(O) symbolizes nor-
malized measurements of property Y for an experiment in
which the initial concentration gradient is entirely in coni-
ponent i (Xi = I ) , measurements corresponding to arbitrary
n
[Is] AY(t)/AY (0) = 2 X,AY,(t)/AY;(O)
i= l
A detailed example is given later.
In order to establish the initial conditions that reduce the
diffusion equations to diagonal form, the standard deviation of
measured values of the apparent diffusion coefficient
may be evaluated as a function of Xi. D, is the mean apparent
diffusion coefficient
N
[I71 B, = N - ' 2 &(ti)
,=I
 478 CAN. J. CHEM. VOL. 63. 1985
For the particular initial conditions Xi'"', the apparent diffusion
coefficient is effectively constant over the duration of a run,
and hence u,-,is minimized. Therefore, values of Xi".' may be
obtained from the positions of the minima in u,]. Eigenvalue DL
is obtained from the mean value of the apparent diffusion
coefficient evaluated at x , ' ~ ' .
Tenjury cllffilsiorl (11 = 2)
When the standard deviation of the apparent diffusion coef-
ficient for a ternary system is plotted against X I , minima are
found at XI"' and XIe'. Since XI + X? = 1, we have
The mean diffusion coefficients evaluated at XI"' and XI"' equal
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 84.78.191.92 on 04/09/11
eigenvalues D l and D,, respectively. The ternary diffusion
coefficients are evaluated from eq. [ 141.
3. Experimental
Ternary diffusion coefficients of dilute aqueous NaOH + NaCl
mixtures were measured at 25°C using a simplified version (14) of
Harned's conductimetric procedure (30). In this technique, initial
concentration gradients are formed by introducing a small volume of
electrolyte into the bottom of a column of solution. The rate of dif-
For personal use only.
fusion is followed by monitoring changes in electrical conductance
measured near the top and bottom of the column.
Because Harned's technique employs very small concentration gra-
dients. changes in the transport coefficients due to compositional
changes along the diffusion column are negligible, and the measured
diffusion coefficients correspond to differential values defined by eq.
[ I ] . (For diaphragm ccll results (31). and to a lesser extent for optical
results (32, 33). small but troublesome corrections arc required to
allow for the concentration-dependence of the diffusion coefficients.)
Moreover, the conductirnetric technique is reliable at low ionic
strength where the transport coefficients can be estimated from lim-
iting ionic conductances (14). Comparison of measured diffusion co-
efficients with theoretical predictions will provide a check on the
reliability of the proposed eigcnvaluc method.
Eq~tiprnerlrarid procedure
The diffusion cells used in this work had cylindrical diffusion chan-
nels (height 0.04560 m, diameter 0.0126 m). The cells were con-
structed from high density polyethylene rather than glass in order to
resist leaching by hydroxide. Pairs of circular platinum electrodes
-
(diameter lo-' m, ccll constant k 10' m-I) werc positioned at levels
one-sixth of the distance from the top and bottom.of the channel. At
the start of each experiment, 0.1-0.3 mL of electrolyte was carefully
injected with a calibrated syringe into the bottom of each solution-
filled chamber. Initial concentration differences across the diffusion
boundary were 0.05-0.2 mol L-I. Conductances were measured six
times per day for four consecutive days beginning one day aftcr
injection of electrolyte. Further details of the equipment and procedure
have been reported (14. 34). Cell constants were obtained by cali-
bration with 0.01 mol L-' aqueous KC1 (conductance 0.01413 m' S
mol-' (35)). Values of S I and S2 were determined using an auxiliary
conductance cell.
Reagents
Reagent grade NaCl was dried in a vacuum oven at 140°C and used
without further purification. Stock solutions of NaOH werc prepared
by diluting saturated solutions that had been filtered to remove in-
soluble darbonate. The NaOH solutions werc stored in polyethylene
bottles and protected from the atmosphere. Concentrations of NaOH
were determined by titration against potassium hydrogen pthalate.
Winkler analyses (36) before and aftcr the experiments indicated that
the solutions contained less than 0.05% carbonate based on total
alkali. Water used to make up the solutions was doubly-distilled and
deionized (conductivity 0.8 X 10." ohm-' m- I). Corrections for
solvent conductance were negligible.
Data arzcr!\~.si.s
For binary diffusion in a Harncd cell, the difference in electrolyte
concentration between the top (T) and bottom (B) electrode positions
is given by (30)
[20] Ac(r) = c,(r) - c.,.(r) = C exp (-T'D~/N')
whcre C is a constant, D is the binary diffusion coefficient, r is the
time elapsed since introduction of electrolyte, and n is the height of the
diffusion channel. For strong electrolytes. Ac(r) is directly propor-
tional to the conductance difference defined by (14, 21, 30)
where kB/kT denotes the ratio of cell constants of the top and bottom
electrode pairs. Values of D are conveniently determined from the
difference equation
by pairing each conductance reading with the corresponding reading
taken on the following day.
In order to determine ternary diffusion coefficients, conductance
differences AKl(r) and AKZ(r)were measured for experiments run
with the initial concentration gradient entirely in NaOH (XI = I) or
NaCl (X, = O), respectively. Apparent diffusion coefficients for initial
condition XI were calculated using the difference equation
wherein
4. Results and discussion
Diffusion coefficients for NaOH(c,) + NaCI(c,) + H,O
mixtures were measured at a total electrolyte concentration of
0.020 mol L-I for ratios of c, :c2 equal to 1 :3, 1 : 1, and 3 : I .
Paired experiments with the initial concentration gradient in
NaOH or NaCl were carried out in triplicate at each of the three
compositions studied.
Typical results for a pair of experiments for e l = 0.0150 and
c, = 0.0050 mol L-' are shown in Figs. I and 2. In Fig. I,
values of the apparent diffusion coefficient computed from eq.
[23] are plotted against t for various initial conditions. It is
evident from the figure that the apparent diffusion coefficient
varies substantially over the duration of a run when the initial
concentration gradient is entirely in NaOH or NaCl (XI = I and
X, = 0 , respectively). It may be noted, however, that values of
D,(t) are essentially constant for values of XI near 0 . 6 and 1.2.
The "stationary" values of D;,(t) (the eigenvalues of D) were
found by plotting the standard deviation of the apparent dif-
fusion coefficients against X I , the fraction of the conductance
difference across the initial diffusion boundary due to NaOH.
From the two minima in u,, shown in Fig. 2, initial conditions
XIo' = 1.21 and X,"' = 0.64 that diagonalize D were obtained.
From the mean apparent diffusion coefficients evaluated at
these two values of X I , eigenvalues D l = 2.58 X 1 0 - 5 n d D,
= 1.71 X lo-' m' s-I were obtained.
The results of the experiments are summarized in Tables 1
and 2. As shown in Table 2, values of D , , , the ternary dif-
 LEAIST AND NOULTY
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FIG. 1. Apparent binary diffusion coefficients of aqueous NaOH(1) + NaCl(2) for el = 0.015 rnol L-' and cz = 0.005 rnol L-' for selected
initial conditions. For the experiment with the initial concentration gradient entirely in NaCl (XI = 0). 0.32 mL of solution containing 0.015
rnol L-' NaOH and 0.0712 rnol L-' NaCl was injected into a cell filled with solution containing 0.015 rnol L-' NaOH and 0.001 rnol L-' NaCI.
For the experiment with the initial gradient in NaOH (XI = I ) , 0.32 mL of solution containing 0.254 mol L-.' NaOH and 0.005 mol L-' NaCl
was injected into the same cell filled with 0.001 rnol L-' NaOH and 0.005 rnol L-' NaCI. The curves for X I = 0.4, 0.64, 0.80, 1.15, 1.21,
and 1.25 were obtained by analysis of linear combinations of data from the two experiments run with X I = 0.00 and X I = 1.00. The volume
of the cell was 5.78 mL.
For personal use only.

FIG.2. Standard deviation of the apparent diffusion coefficient of aqueous NaOH(1) + NaCl(2) for el = 0.015 mol L-' and c1 = 0.005 rnol
L-'. See caption of Fig. I for details.

fusivity of NaOH in aqueous NaCI, increase steadily as the
system becomes richer in NaCI. At the same ionic strength, in
contrast, the binary diffusivity of aqueous NaOH is only 1.99
x lo-' mm? s-' (34). In binary solutions of NaOH, however, the
condition of electroneutralitv reauires that Nat and OH- dif-
d .
fuse at the same rate, even though OH- has approximately four
times the mobility of Naf (35); the electric field produced by
flow of the electrolyte slows down OH- and speeds up Naf so
that they travel at the same rate and the electric current is zero.
In ternary NaOH(1) + NaCl(2) + Hm?O mixtures, on the other
hand, the electric field along the NaOH gradient which slows
down OH- also generates counterflow of C1-. Highly mobile
OH- can thus diffuse down the NaOH gradient more rapidly
than Naf while still maintaining electroneutrality. This mech-
anism accounts for the increased diffusivity of the NaOH com-
ponent in aqueous NaCl as well as the large negative values of
Dm?, (the cross-diffusion coefficient measuring coupled flow of
NaCl produced per unit concentration gradient in NaOH). Sim-
ilar diffusional behavior has been observed for HCI + NaCl +
H 2 0 and other acid-containing mixed electrolytes (6, 8, 21). In
those systems, the electric field generated by diffusion of high-
ly mobile protons produces counterflow of cations.
 C A N . J. CHEM. VOL. 63. 1985

TABLEI. Parameters used to calculate experimental diffusion coefficients for NaOH( I ) +

NaCl(2) + HZ0 at 25°C
(.I(( c.2 SI/SZ x,"' XI"' D," D:

" I n lo-' mol L-'

lo-.*J ",? 1.

2. Observcd and predicted ternary diffusion coefficients for NaOH(1) + NaCl(2) + H20
TABLE
at 25°C
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5.0 15.0 Obsd. 3.72 (k0.02) -0.30 (20.04) - 1.34 (20.13) 1.76 ("0.03)
Calcd. 3.70 -0.23 - 1.29 1.7 1
10.0 10.0 Obsd. 2.95 (k0.19) -0.33 (20.07) -0.71 (20.21) 1.70 (20.10)
Calcd. 2.93 -0.37 -0.7 1 1.82
15.0 5.0 Obsd. 2.42 (k0.07) -0.52 (20.01) -0.31 (20.10) 1.90 (k0.01)
Calcd. 2.39 -0.47 -0.30 1.89
"In lo-.' mol L - '
l'ln 10-9 ",'

TABLE
3. Comparison of obscrved and predicted LiLcoefficients

(.;' RTL, ," RTL Iz" RTL?," RTL~?~

For personal use only.

5.0 15.0 0bsd. 1 .69 (20.02) -0.94 (20.04) -0.90 *O 1.94 (50.05)
Calcd. 1.67 -0.87 -0.87 1.89
10.0 10.0 Obsd. 2.18 (20.16) -0.94 (k0.09) -0.94 (k0.18) 1.47 (k0.12)
Calcd. 2.33 -0.97 -0.97 1.55
15.0 5.0 Obsd. 2.27 (k0.09) -0.65 (k0.05) -0.64 (k0.10) 0.89 (k0.02)
Calcd. 2.41 -0.625 -0.625 0.89
" I n lo-.' mol L-I.
" I n 10.'' niol m-' s-I

The difference in mobility between Na' and C I is not as TABLE

4. Molar ionic conductances and
great as the difference in mobility between Nai and OH-: C1- other parameters" used to calculate the-
is about 50% more mobile than Na ' (35). The electric field per oretical valucs for the transport coefficients
unit concentration gradient in NaCl is therefore weaker than for
NaOH, and values of D l , for aqueous NaOH(1) + NaCl(2) are Electrolyte A , AO,,,' P"
proportionally smaller than for D 2 ]Also, the increase in the NaOH 50.10 198.3 0.08"
diffusivity D,, of NaCl in NaOH-rich mixtures is not as dra- NaCl 50.10 76.35 0.16'
matic as for D l , in NaC1-rich mixtures.
Onsager's equations (25) "Ion size parameter (14) a = 4 X lo-"' ni;
n
solvent viscosity (35) q = 8.90 X lo-' kg m-'
s-I; solvent dielectric constant (35) E = 78.4;
[251 J , = - 2 L,LVFL Debye-Hiickel constant (35) a = 1.17.
I= I "Reference 34.
relate molar fluxes, J i , of components to gradients in the chem- ' Reference 39.
"In lo-' m' s mol'.
ical potentials of the components. Conveniently, values for the " I n L mol-I.
L,, phenomenological coefficients can be estimated (14) for
dilute mixed electrolytes from limiting ionic conductances and
Onsager-Fuoss theory (37, 38) of the electrophoretic and re-
laxation effects. Details of the calculations have been reported
(14). Given L, values, diffusion coefficients are calculated
from (25) for the chemical potentials of the solutes. Mean ionic activity
n coefficients (on the molar concentration scale) were evaluated
[261 Dik = 2 L,,,, p,,,/a using Guggenheim's expression (39)
111 = I

The parameters used to predict the transport coefficients of [29] In y,; = -a

vet + c2 + p l c l + pzcz + p,(el + c*)
+
aqueous NaOH(1) NaCI(2) are listed in Table 4. Values of I +-
dp,,,/dc, were calculated by differentiation of expressions where ci is the Debye-Hiickel constant and are small empir-
 LEAIST A N D NOULTY

TABLE 5. Experimental diffusion coefficients for NaOH(I) + NaCl(2) + H,O at 25OC

determined by non-linear least squares

" I n lo-' mol L- '

10-0 m' s - l ,

ical constants which allow for specific ion interactions. 1. E. L. CUSSLER.Multicomponent diffusion. Elsevier, Am-
Experimental transport coefficients are compared with pre- sterdam. 1976.
dicted values in Tables 2 and 3. Agreement is very good. The 2. L. ONSACER. Ann. N. Y. Acad. Sci. 46, 241 (1945).
3. V. VITACLIANO and R. SARTOKIO. J . Phys. Chem. 74, 2949
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 84.78.191.92 on 04/09/11

observed values of the L,, coefficients are consistent with the

Onsager reciprocal relation (2, 25) L,? = L?, which lends fur- ( 1 970).
4. R. P. WENDT.J . Phys. Chem. 69, 1227 (1965).
ther confidence to the reliability of the eigenvalue method. 5. P. J . DUNLOP. J . Phys. Chem. 63, 612 (1959).
A general procedure for the determination of ternary dif- 6. H. KIM,G. REINFELDS, and L. J . GOSTING. J . Phys. Chem. 77,
fusion coefficients from conductance measurements using non- 934 ( 1973).
linear least squares has been reported (40). In practice, we 7. D. G. LEAIST. J . Chem. Soc. Faraday Trans. I. 78, 3069 (1982).
found that the eigenvalue method was much easier to use. The 8. A. REVZIN. J . Phys. Chem. 76, 3419 (1972).
non-linear least-squares procedure, for instance, requires 9. Ref. I, Chapt. 4.
lengthy computations in order to simultaneously optimize val- 10. P. J. DUNLOP, B. J . STEEL,and J . E. LANE.Experimental meth-
ues of the four diffusion coefficients. Experimental diffusion ods studying diffusion in liquids, gases, and solids. In Physical
coefficients determined for NaOH + NaCl mixtures by the methods of chemistry. Vol. I. Edited by A. Weissberger and
B. W. Rossiter. Wiley, New York. 1972. p. 205.
non-linear least-squares method are given in Table 5. Com-
l I. H. FUJITA and L. J. GOSTINC. J . Phys. Chem. 64, 1256 (1960).
parison of Tables 2 and 5 indicates that the eigenvalue and
For personal use only.

12. J . G. ALBRICHT and B. C. SHERRIL. J. Solution Chem. 8, 201

non-linear least-squares procedures give essentially identical (1979).
results. With the eigenvalue method, however, the problem of 13. D. G. MILLER. J . Solution Chem. 10, 83 1 ( 1 98 1).
locating the minimum in the variance in four dimensions is 14. D. G. LEAISTand P. A. LYONS.Aust. J . Chem. 33, 1869 (1980).
replaced by the more manageable problem of locating two 15. E. L. CUSSLERand P. J . DUNLOP. J . Phys. Chem. 70, 1880
minima in one dimension (i.e. minima in cr, as a function of ( I 966).
XI). 16. G. K O ~ A N O V and I C HH. T. CULLINAN. Can. J . Chem. Eng. 49,
In effect, the eigenvalue method reduces the analysis of 753 (1971).
coupled, multicomponent transport equations to an analysis 17. H. KIM.J . Phys. Chem. 73, 1716 (1969).
18. H. L. TOOR.A. 1. Ch. E. J . 10, 448 (1964); 10, 460 (1964).
based on de-coupled, well-understood binary equations. This
19. W. E. STEWART and R. PROBER.lnd. Eng. Chem. Fundam. 3,
transformation enables the determination of ternary dif- 224 ( 1 964).
fusivities without explicitly solving multicomponent diffusion 20. H. MARCENAU and G. M. MURPHY. The mathematics of physics
equations or resorting to non-linear curve fitting procedures. and chemistry. 2nd ed. Van Nostrand, New York. 1956. p. 320.
The eigenvalue method holds especial promise for the mea- 21. D. G. LEAIST and P. A. LYONS.J . Phys. Chern. 86, 564 (1982).
surement of quaternary diffusion (17). For those systems, the 22. E. M. CHOY,D. F. EVANS, and E. L. CUSSLER. J . Am. Chem.
non-linear least-squares method requires simultaneous opti- SOC.96, 7085 (1974).
mization of nine parameters (a formidable task), while the 23. R. M. IZAIT, D. V. DEARDEN, D. W. MCBRIDE,J . L. OS-
eigenvalue method would involve searching for three minima CARSON,J . D. LAMB,and J . J . CHRISTENSEN. Sep. Sci. Technol.
in only two dimensions. 18, I I I3 (1983).
24. N. N . LI and A. L. SHRIER. It1 Recent advances in separation
The present study has employed time invariance of the ap-
science. CRC Press, Cleveland. 1972. p. 163.
parent diffusion coefficient to locate the eigenvalues of D. This 25. S. R. DE GROOTand P. MAZUR.Non-equilibrium thermo-
criterion is well suited to the Harned technique and other re- dynamics. North-Holland, Amsterdam. 1962.
stricted diffusion experiments ( 1, 4 1) in which the concen- 26. F. T. WALL,P. F. GRIEGER, and C. W. CHILDERS. J . Am. Chem.
trations are measured at two positions along the path of dif- SOC.74, 3562 (1952).
fusion. On the other hand, optical methods (4-6, 8- 13) such 27. M. TANICAKI, K. KONDO,M. HARADA,and W. ECUCHL.
as Rayleigh o r Gouy experiments employ free diffusion bound- J . Phys. Chem. 87, 586 (1983).
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