Interdiffusion of acids and bases.

HCl and NaOH in aqueous solution

'

DEREKG. LEAIST AND BETTYWIENS

Department of Chemistry, University of Western Ontario, London, Ont., Canada N6A 5B7
Received November 12, 1985

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DEREKG . LEAIST
and BETTY
WIENS.Can. J. Chem. 64, 1007 (1986).
Stokes magnetically stirred diaphragm cells have been used to measure interdiffusion of hydrochloric acid and sodium
hydroxide in aqueous solution at 25OC. Expressions are developed to estimate ternary diffusion coefficients for these mixtures.
The analysis reveals sharp discontinuities between the diffusion properties of HC1-rich and NaOH-rich mixtures. Although the
diffusion coefficients are sensitive to concentration, accurate analytic approximations for rates of interdiffusion can be obtained
by averaging coefficients along the diffusion path. When HCI and NaOH interdiffuse, proton-coupled and hydroxide-coupled
diffusion operating simultaneously on opposite sides of the diffusion boundary lead to rapid diffusion of inert Na' and C1species.

DEREK
G. LEAIST
and BETTY
WIENS.Can. J. Chem. 64, 1007 (1986).
On a utilisk des cellules i diaphragme de Stokes agitkes d'une faqon magnktique pour mesurer l'interdiffusion de l'acide
chlorhydrique et de l'hydroxyde de sodium dans des solutions aqueuses i 25C. On a dkveloppt des expressions mathematiques
pour Cvaluer les coefficients de diffusion ternaire pour ces melanges. L'analyse rkv&leI'existence de discontinuites marquees
entre les propriktks de diffusion de melanges riches soit en HCl ou en NaOH. MCme si les coefficients de diffusion sont sensibles i
la concentration, on peut obtenir des approximations analytiques assez precises pour les vitesses d'interdiffusion si l'on fait des
moyennes des coefficients le long du chemin de diffusion. Lorsqu'il se produit de l'interdiffusion du HCl et du NaOH, des
diffusions likes soit au proton ou h l'hydroxyde qui op&rentsimultanCmentde chaque c6t6 de la frontihe de diffusion provoquent
la diffusion rapide d'espbces Na+ et C1- inertes.
[Traduit par la revue]

1. Introduction
Interdiffusion of acids and bases occurs in many important
absorption, extraction, and leaching operations. Transport in
these and other reactive electrolyte mixtures is usually described
by solving the Nernst-Planck equations (1, 2).

for the concentrations ci of each diffusing species. Reaction

rates per unit volume, ri, are included for species produced
or consumed by chemical reactions. The diffusion-induced
electric field (E) couples transport of charged species. As a
result of these complications, Nernst-Planck equations are
difficult to solve. Solutions are usually obtained numerically by
finite difference approximations (3, 4).
This research was undertaken to test a simpler treatment of
acid-base diffusion, multicomponent Fick equations (5, 6)

which are phrased in terms of total concentrations Ci of neutral

electrolyte components (such as HCl and NaOH) rather than
concentrations ci of charged species (such as H+, C1-, Na+, and
OH-). This approach offers several advantages:
( a ) Fewer differential equations are required.
( b ) Because total (reacted plus unreacted) components are
conserved, reaction rate terms ri can be dropped.
(c) Since the components are electrically neutral, it is not
necessary to evaluate the electric field. (The effects of E
are included implicitly in the values of the multicomponent
diffusion coefficients.)
( d ) If the diffusion coefficients are constant, or if suitable
average coefficients can be defined, eq. [2] simplifies to
'To whom all correspondence should be addressed.

for which analytic solutions exist.

To illustrate these ideas, we develop expressions to estimate
multicomponent diffusion coefficients for aqueous hydrochloric
acid + sodium hydroxide mixtures. Rates of diffusion for these
mixtures predicted by multicomponent diffusion equations are
then compared with rates measured by diaphragm cell experiments.

2. Experimental
Diffusion was measured by the Stokes diaphragm cell method (7).
In these experiments solute diffuses between upper and lower magnetically stirred cell compartments through the pores of a sintered glass
disc. The rate of diffusion is determined from changes in solute
concentration after the cells are run for a timed interval.
Fine porosity pyrex diaphragms (3 cm diameter, 0.2 cm thick, mean
pore diameter 5 x
cm) were used in this work. Cell compartment
volumes (25-35 cm3) of each cell were matched to within 0.5%. Each
compartment was fitted with a greaseless teflon stopcock and a glasscoated iron stirrer which was rotated once per second by external
magnets. Each cell was calibrated at frequent intervals by diffusing
0.5 M KC1 into pure water at 25OC. Cell constants P (0.16-0.20 ~ m - ~ )
were computed from the relation
[41

Ac(t) = Ac(0) exp (-PD t)

where Ac(t) is the measured difference in KC1 concentration between

upper and lower compartments at time t. The integral diffusion
coefficient of aqueous KC1 ( D ) was evaluated by interpolation of the
data reported by Stokes (8).
At the start of each experiment the lower compartment was filled
with a binary solution of aqueous HCI or NaOH, whicheverwas denser.
The upper compartment was filled with a binary solution of the other
component. The cells were placed in a thermostat at 25 + O.OlC and
stirred for about 2 h to establish steady state diffusion through the
diaphragms. The cell compartments were rinsed, refilled with fresh
solution, then returned to the thermostat for the duration of the run
(0.2-5 days). Initial and final solute concentrations were determined

1008

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by potentiometric titration against silver nitrate and standardized HCl

or N a 0 ~ .
Chemical reaction of HCl and NaOH produces heat. To maintain
isothermal conditions during a run, dilute solutions with small heats of
reaction were used. The rate of heat production in each diaphragm was
never more than 1 mW (considerably less near the end of a run). We
estimate the maximum increase in diaphragm temperature was only
0.00l0C.

3. Theory
What is the minimum number of solute flows that must be
specified to give a complete macroscopic description of diffusion in an isothermal electrolyte mixture containing s different
solute species which undergo e chemical reactions? Because
electrolytic reactions are rapid, e chemical equilibria exist
locally. Electroneutrality provides one additional restriction.
Therefore, on& N = s - e - 1 solute concentrations are
independent (9). We may choose N neutral solute components
and describe diffusion of these components by multicomponent
Fick equation [2].
Multicomponent diffusion equations, though simpler than
Nernst-Planck equations, are of little practical use unless
values of multicomponent diffusion coefficients Dikare known.
Fortunately, values of Dikcan be estimated by taking weighted
averages of the diffusion coefficients Di of the various solute
species (9- 12). This well-established procedure is illustrated
in the Appendix for aqueous hydrochloric acid + sodium
hydroxide mixtures.

Hydrochloric acid(1) sodium hydroxide(2) + water (s = 4,

e = 1,N=2)
Four different solute species (H+, C1-, Na+, OH-) are
transported in aqueous HCl + NaOH mixtures. However, the
conditions of chemical equilibrium (H20 H+ + OH-) and
electroneutrality reduce the number of independent solute flows
to only two. Therefore, a concise but complete description of
interdiffusion of HCl and NaOH is given by ternary diffusion
equations

where C1 and C2 denote total concentrations of HCl(1) and

NaOH(2) components in moles per unit volume. Molar flux
dimities of the components are given by

Expressions developed in the Appendix together with the

species diffusion coefficients listed in Table 1 were used to
calculate ternary diffusion coefficients for aqueous HC1
NaOH mixtures at 25C. The results are plotted against solute
fraction of HCl (designated by XI) in Fig. 1.
When HC1 and NaOH interdiffuse, proton-coupled transport
and hydroxide-coupled transport operate simultaneously on
opposite sides of the diffusion boundary. This leads to remarkable diffusion properties, such as rapidly varying diffusion
coefficients, large cross terms, and sharp discontinuities in
diffusion properties. As expected for a strong electrolyte
mixture (12), values of Dik are sensitive to the ratio of solute
concentrations, but not to total solute concentration.
The diffusivity of HCl in aqueous NaOH solutions (Dl])
takes values from 2.0 X lop9 to 6.3 X lop9 m2 s-'. As the
solute fraction of HCl approaches unity, D l l approaches the

TABLE1 . Species diffusion coefficients

at 25C"
Species

D i(lop9m2 s-l)

H+

c1-

Na+
OH"Estimatedfrom published limiting ionic
molar conductances (13) Aoi using the relation Di = RTAoi FZ. F is the Faraday,
96487 C mol-'.

binary diffusivity of aqueous HCl, about 3.0 x lop9 m2 s-I. In

pure aqueous HCl, C1- and highly mobile H+ diffuse at the
same speed; the diffusion-induced electric field slows down H+
and speeds up C1-, thereby preventing charge separation. If
NaOH is added, it reacts with HCl to form NaCl. In the resulting
ternary mixture, H+ can diffuse more rapidly than C1-. Charge
separation is avoided because the electric field established by
the HCl gradient generates counterflow of Na+. This mechanism increases the diffusivity of HCl and leads to large negative
values for DZ1,the cross coefficient that measures coupled flow
of NaOH along the HCl gradient. Because the HCl gradient is
unable to generate flow of NaOH in solutions free of NaOH, D21
+ O a s X , + 1.
There are sham
x suikes in the diffusion coefficients near XI =
0.5. For example, D l l reaches a maximum value of 6.3 x
lop9 m2 s-' at solute fractions of HCl slightly above 0.5 where
all but a trace of HCl is neutralized by NaOH. At these
compositions, transport of HCl corresponds to tracer diffusion
of H+ in supporting NaCl solutions. Therefore, the HCl gradient
VCl produces flow -DH+VCl of H+ with tracer diffusivity
DH+ = 9.3 X loF9 m2 s-'. The HC1 gradient also drives
co-current flow -DllVCl of C1- and counter-current flow
-DZ1VCl of Na+. Electroneutrality requires that D l l - Dzl =
DH+at X1= 0.5+.
At solute fractions of HCl below 0.5, HCl reacts completely
with excess NaOH. The disappearance of free H+ leads to a
sudden drop in the diffusivity of the HCl component. In this
region the HC1 gradient VCl produces an equal but opposite
gradient -VCl in free OH-. At HCl solute fractions just
below 0.5, trace amounts of OH- diffuse in supporting NaCl
solutions. In this case the C1- flux -DllVCl and Na+ flux
-DZ1VCl are balanced by the tracer OH- flux DOH-VCl.
Hence Dll - DZ1= DOH-= 5.3 X 10-9m2 at X1 = 0.5-. In
the limiting case of a trace of HC1 in aqueous NaOH, Dl1
approaches the tracer diffusion coefficient of C1-, about 2.0 x
lop9m2 s-'.
The diffusivity of NaOH in aqueous HC1 solutions, 022,
ranges from 1.3 x lop9 to 4.3 x
m2 s-'. At low solute
fractions of HCl, values of DZ2are close to the binary diffusivity
of aqueous NaOH, about 2.0 x
mP2 s-'. As more HC1 is
added, Dz2 increases. It reaches the value 2.8 X lop9m2 s-I
just below XI = 0.5. At XI = 0.5-, electroneutrality requires
that Dz2 - D12 = DOH-.
In HC1-rich mixtures, proton-coupled transport of Na+ leads
to Dzz values as large as 4.3 x lop9 m2 s-I. A gradient in
concentration of NaOH in an otherwise uniform solution of
excess HCl establishes an equal but opposite gradient in free
H+. As H+ diffuses rapidly towards the zone of higher NaOH
concentration, counterflow of ~ a is+ generated to prevent
L

LEAIST AND W E N S

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C,

0.0

Cz = 0.050 M

0.5

1.O

0.0

0.5
C,/(C,

C,/ (C, + C2)

1.O
C2)

FIG. 1. Ternary diffusion coefficients at 25OC for aqueous HCl(1) + NaOH(2) plotted against HCl solute fraction X1 = C1/(C1 + C2) for
total solute concentrations CI + C2 equal to 0.025, 0.050, and 0.075 M. Activity coefficient terms were included in the calculations.

charge separation. At X1 = 0.5+, DZ2 - D12 = DH+. In the

limit X1+ 1, D22equals the tracer diffusion coefficient of ~ a +
in supporting HC1 solutions, about 1.3 X 1o - m2
~ s- '.

4. Results and discussion

Figure 2 shows diaphragm cell results, for diffusion of 0.025,
0.050, and 0.075 M HC1 into 0.075, 0.050, and 0.025 M
NaOH, respectively. Component concentration differences
across the cell diaphragms are plotted against P t .
The data shown in Fig. 2 can be used to calculate the apparent
binary diffusion coefficients.

for the HCl(1) and NaOH(2) components. When 0.075 M HC1

diffuses into 0.025 M NaOH, for example, the initial slope of
AC1 versus p t corresponds to an apparent diffusivity of HC1
equal to 8 X lop9 m2 s-', an exceptionally large apparent
diffusivity. In this case the HC1 component diffuses rapidly
because the main flow of HC1 (-DllVC1) is reinforced by a
large co-current coupled flow of HCl (-D12VC2) generated by
the NaOH gradient. As further evidence for strongly coupled
diffusion, note that the concentration difference for the HCl
component can change sign. When this happens, the cell
compartment that held no HC1 at the start of the experiment now
contains more HC1 than the compartment which initially held
all of the HCl. Thus HC1 has diffused "up" its concentration
gradient.
If the diffusion coefficients are constant, integration of the
ternary diffusion equations gives simple analytic expressions (14)

5
-

FIG. 2. Comparison of experimental and calculated concentration

differences between upper and lower cell compartments for interdiffusion of HCI(1) and NaOH(2) compartments:
diffusion of
0.025 M HC1 into 0.075 M NaOH; a, 0.05 M HCI into 0.05 M
NaOH; 0, 0.075 M HCl into 0.025 M NaOH. The plotted curves
give concentration differences calculated from eqs. [8] using integral
diffusion coefficients listed in Table 1.

+,

1010

CAN. 1. CHEM.VOL. 64, 1986

TABLE
2. Integral diffusion coefficients for aqueous HCI(1) + NaOH(2)"

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"ACi(0)and bikin units of M and

mZ s-', respectively.

[8a]

ACl(t)/ACI(0) = Al exp (-PD)(')t)

+ (1 - A]) exp (-PD(')t)

[8b]

AC2(t)/AC2(0) = (1 - A2) exp (-PD(')t)

+ A, exp (-PD(')t)

for the concentration differences across the cell diaphragms.

D") and D(') denote eigenvalues of the diffusion coefficients
matrix

1. W. NERNST.
Z. Phys Chem. Stoechiom. Verwandtschaftsl. 2,
613 (1888); 4, 129 (1889).
2. M. PLANCK.
Ann. Phys. (Leipzig), 40, 561 (1890).
3. A. EKMAN,
S. LIUKKONEN,
and K. KONTTURI.
Electrochim.
Acta, 23, 243 (1978).
4. J. GARRIDO,
S. MAFE,and J. PELLICER.
J. Membr. Sci. 24, 7
(1985).
and K. R. HARRIS.
Diffusion in liquids.
5. H. J. V. TYRRELL
Butterworth, London. 1984. Chapt. 3.
6. D. D. FITTS.Nonequilibrium thermodynamics. McGraw-Hill,
New York. 1962. Chapts. 7 and 8.
J. Am. Chem. Soc. 72,763 (1950).
7. R. H. STOKES.
8. It. H. STOKES.
J. Am. Chem. Soc. 73, 3527 (1951).
J. Chem. Soc. Faraday Trans. 1,78,3069 (1982).
9. D. G. LEAIST.
J. Phys. Chem. 89, 1486 (1985).
10. D. G. LEAIST.
11. D. G. LEAIST.
Aust. J. Chem. 38, 249 (1985).
and P. A. LYONS.
J. Phys Chem. 86, 564 (1982).
12. D. G. LEAIST
13. R. A. ROBINSON
and R. H. STOKES.
Electrolyte solutions. 2nded.
Academic Press, New York. 1959. App. 6.2.
and P. J. DUNLOP.
J. Phys Chem. 70, 1880
14. E. L. CUSSLER
(1966).
15. A. R. GORDON.
AM. N.Y. Acad. Sci. 46, 285 (1945).
16. E. A. GUCGENHEIM
and J. C. TURGEON.
Trans. Faraday Soc. 51,
747 (1955).

Appendix
The purpose of this appendix is to derive expressions for
estimating ternary diffusion coefficients for aqueous HC1 +
NaOH mixtures. We will use the identity (5, 6)

Constants Ai are given by

Unhappily, diffusion coefficients for HC1 + NaOH mixtures

change by several hundred percent and pass through sharp
discontinuities along the diffusion path. This rules out any hope
of obtaining exact analytic descriptions of diffusion. However,
it is helpful to define mean integral diffusion coefficients (15)

'AIL
where X 1L and jZ 1U denote mean solute -fractions in the lower
(L) and upper (U) compartments, i.e., X 1U = [XIU(t=0) +
Xlu(t=w)]/2. Values of Dik calculated in this manner are
listed in Table 2. Upon substitution of mean integral diffusion
coefficients into eqs. [8], one obtains the calculated values for
ACl(t) and AC2(t) given by the solid curves in Fig. 2.
Experimental and calculated concentration differences are in
close agreement. This comparison suggests that the calculated
ternary diffusion coefficients correctly describe interdiffusion
of HCl and NaOH. The calculated concentration differences
corroborate negative experimental values for AC1.
In conclusion, multicomponent diffusion equations provide
accurate analytic descriptions of interdiffusion of acids and
bases, a convenient alternative to finite difference a ~ ~ r o x i m a tions .to the Nernst-Planck equations. The multicomponent
analysis also provides direct information about the diffusivity of
each electrolyte and the importance of coupled transport of other
electrolytes in the mixture.

where k m are the chemical potentials of the components. Lim

are Onsager transport coefficients defined by flow equations for
the components
2

[A21

-Ji =

[A31

-j.I = l..Vb.
II
I

LimVkm
m=l
According to the Nernst-Planck approximation, the flow of
each species is proportional to the gradient in its electrochemical
potential
where lii = ciDi/RT. R is the gas constant and T is the
temperature. We number the solute species in aqueous HCl(1)
+ NaOH(2) as follows: C1- = 1, Na+ = 2, H+ = 3, and OH- =
4.
The flux of the HC1 component equals the flux of C1-. Also,
the flux of the NaOH component equals the flux of Na+.
[A41
[A51

J1(HCl) = jl (Cl-)
J2(NaOH) = j2(Na+)

The gradients in chemical potential of each component equals

the sum of the gradients in electrochemical potential of the
constituent species

L L

5. Acknowledgement
The authors gratefully acknowledge financial support by the
Natural Sciences and Engineering Research Council of Canada.

[A61

VkI(HC1) = Vb1(C1-) + Vb3(H+)

Vk2(NaOH) = Vb2(Na+) + Vp4(OH-)

[A71
Electroneutrality and local chemical equilibrium of H+ and
OH- provide t6e relations

+ j4(OH-)

[A81

jl(C1-)

[A91

Vb3 + Vb4 = 0

= j2(Na+)

+ j3(H+)

1011

LEAIST AND WlENS

Substitution of eqs. [A3]-[A91 into eq. [A21 gives

1'
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I1

:
1

[All] RTLlz = RTLzl = clDlczDz/A

D ~ + cqD4)/A
[A121 RTLZ2= c ~ D ~ ( c+~c3D3
where A stands for
The component chemical potentials are given by the expressions

+ Ill2)

where I is the ionic strength and Sf = 1.17 for aqueous solutions

at 25C.

:
j

[A221 Dl2 = tl (D2 - D3)

/i

[A171 In yi = -sg?I1l2/(1

Finally, expressions for the ternary diffusion coefficients may

be obtained by substituion of eqs. [A10]-[A121 and [A18][A201 into eq. [All. If activity coefficient terms are omitted,
the expressions for D,k simplify considerably,

[A231 D21 = t ~ ( D 1- D3)

[A141 pl(HC1) = ~ ~ ( H c +
I )RTln [c3(Ht)c1(Cl-)y3yl]
[A151 p2(NaOH) = p i ( N a 0 ~ )
[A241 Dzz = t2D3 + (1 - t2)D2
+ RT In [ ~ z ( N ~ + ) ~ ~ ( O H - ) YHere
Z Y t,~ refers to the transference number of ion i defined by
in which yi are ionic activity coefficients (molar concentration
[A251 ti =
ckzk2~x
scale). Concentrations of H+ and OH- are related by
k= 1
[A161 Kw = c ~ ( H + ) c ~ ( ~ H - ) Y ~ Y ~
Excess NaOH (C2 > CI)
where Kwis the dissociation constant for water. We will assume
When excess NaOH is present, (Cl- ) = Cl , c2(Na+)= C2
that the activity coefficients are given by the Debye-Hiickel
as before, but c4(0H-) = C2 - C1 and C3(H+)= Kw/(C2 equation (16)
C1)y3y4= 0. Expressions for derivatives ap,/aCk for these

/
i
!

~ (/ ~
a ~ ~) - l a p =
~ /( ca2 ~- ~c l ) - l
[~19]( ~ ~ ) - l a p =

Excess HCl (C > C7)

or mixtu;esZcontainingexcess H C ~cl: (Cl-) = C1, c2(Na+)
= C Z ,c3(H+) = CI - C2 and c4(0H-) = Kw/(CI - C2)y3y4
= 0. Differentiation provides

solutions can be obtained by interchanging subscripts 1 and 2

in eqs . [A 181 and [A 191.
If activity coefficientconections are dropped, we obtain

A,

C~
[A181 ( ~ ~ ) - l a p ~ /=a C1-l

+ (CI - C2)-'

[A271 Dl2

tl (D2 - 04)

[A281 Dzi = t2(D1 - 04)

[A291 DZ2= t2D4 + (1 - t2)D2