Journal o f Solution Chemistry, VoL 8, No.

12, 1979

The Viscosity of Aqueous Electrolyte

Solutions and the TTG Model
J. V. Leyendekkers ~
Received March 27, 1979; revised M a y 29, 1979

An equation covering the dynamic viscosity from zero to high concentrations

has been derived on the basis o f the TTG model. The equation is compatible
with the Eyring and NMR theories and has a similar form to the Othmer-rule
equation. A component o f the limiting viscosity slope is shown to be propor-
tional to the Falkenhagen slope. The TTG equation was tested for 20 electro-
lytes o f diverse charge type and found to fit the data within the experimental
errors. The equation is simply extended to cover pressure, temperature, and
component changes. The viscosities o f three multicomponent systems are
predicted to within the experimental errors. The derived parameters o f the
equation were found to be simply related to the TTG volume o f the solute.

KEY WORDS: Viscosity; aqueous electrolyte; Tammann-Tait-Gibson

model.

1. I N T R O D U C T I O N
Erdey.Gruz <1~ and Stokes and Mills ~2~ have discussed in detail the various
theories and empirical correlations for the dynamic viscosity of aqueous
solutions. Kay ~3~and Kell ~4~have given interesting discussions related to the
viscosity of aqueous electrolyte solutions and water, respectively. In particular
Kay ~3~has brought out the critical importance of ion-solvent interactions in
formulating successful ion transport theories.
The dilute solution theories of viscosity are not practicable because of
their very restricted range (0-0.1 m). On the other hand, the equations used
for the moderate to high concentrations are usually '~best-fit" type equations
and do not extend to the dilute solution range. The latter also applies when
models have been used. ~5-9~ The work of Angell and Bressel ~1~ may be
considered an exception. These authors developed a quasi-empirical equation

1 School of Biological Sciences, Building A12, University of Sydney, 2006, N.S.W.

Australia.
853
0095-9782[79[1200.0853503.00[0 9 1979PlenumPublishingCorporation
854 Leyendekkers

(using the liquid "hole" concepts) covering the concentration range 0-26
moleTo for Ca(NO3)2. More recently, Maisano et al. ~ developed a model for
NiC12 solutions with a similar emphasis on structural properties. The equa-
tions from these two studies indicate discontinuities which do not seem
compatible with nuclear magnetic resonance (NMR) studies/~2> In any case,
the models were developed for single electrolytes and cannot be considered as
general.
In the present paper the Tammann-Tait-Gibson (TTG) model is applied
to viscosity in order to develop an equation covering zero to high (near or at
saturation) concentrations. Twenty electrolytes of diverse charge type are
considered. The derived equation covers changes in temperature and pressure
and is simply extended to multicomponent solutions. The general principles
of the TTG model have been outlined previously ~13-15~ and only aspects
relevant to viscosity are given here.

2. TTG EQUATIONS
The main hypothesis of the TTG model is that the effect of the ionic
size, shape, and charge on the water is equivalent to the effect of an applied
pressure (the effective pressure pc) which changes the volume of the water to
the "apparent" volume, ~bw.The volume ~14~of the salt in the solution, ~b~,is
negligibly affected by pressure. This hypothesis enables the comptex ion-
solvent interactions (including, e.g., hydrolysis) to be simply and quantita-
tively accounted for. In applying the model to any solution property, the
water-in-solution contribution is first calculated from the p~ function and
data for pure water under pressure. The residual function of the solution
property should then be simply related to the concentration and to the intrin-
sic properties of the salts. The pe function is a general function which applies
to all solution properties whereas the residual function is specific to the
individual property: For all the properties studied so far (density, refractive
index, heat capacity) it has been found that only one or two TTG parameters
are necessary for the residual function, which characterizes the solution
property from zero to high concentrations.~1a-16~

2.1. General Equation

In the case of viscosity the various published theories and empirical
correlations ~1~indicate an equation of the form
In (W~fiTwls)= f ( m ) (1)
to be the most suitable for application of the TTG model. The symbols
% and ~Twi~represent the viscosities of the solution and the water in solution,
respectively, and m is the concentration (moles/kg water).
Viscosity of Aqueous Electrolyte Solutions and the TTG Model 855

Equation (1) can be interpreted to mean that at a given temperature the

difference in the phenomenological activation volumes (4) of the solution and
the water in solution is a simple function of the concentration. As noted
above, it can be expected that the parameters off(m), the TTG parameters,
will be simple functions of the solute properties, in this case the TTG volume.
The value of ~Twlsis given by
wl~ (2)
where ~ is the viscosity of pure water, p is the external pressure, andpe is the
effective pressure due to the salt. The value of pe is calculated from
ps = ho + h l x + h2x 2 + hax a (3)
where x is the concentration of the solute in grams per gram of solution and
the h parameters are functions of temperature but independent of pressure.
The values of these parameters for a range of electrolytes at 20 and 25~ have
been given previously. (14-~6) The value of h0 is zero within the experimental
errors.
The viscosity of pure water as a function of temperature and pressure
is given by the recent IAPS (International Association for the Properties of
Steam) equation (z~) which has the form

~w = ~/o e x p [ d =~oj~=ob~J( ~ - 1 ) i ( d , - 1)J l (4)

with
-1
7o = \T~] ak (in Pa-sec, or 103 cP) (4a)

where T* = 647.27~ and d* = 317.763 kg-m-3; Tand dare the temperature

and density respectively (with units corresponding to T* and d*). The b
coefficients are given in ref. 17. At 20~ Eq. (4) is valid up to 10,000 bars
(1,000 MPa). The values of ~/wat 20~ calculated from Eq. (4) agree with the
experimental data of Stanley et al. (18) to better than 0.1~ up to 500 bars. The
latter data are increasingly higher up to 1400 bars (they increase by ca. 0,1570
per 200 bars to reach a deviation of 1~o from the IAPS value at 1400 bars).
Stanley et al.'s data extend only to 1379 bars, and are summarized by
(~7~)/~))2ooc = 0.99957 - 0.341722 x 10-4p
+0.277740 • 10-6p 2 std. dev. +0.0008 (5)
with p the total pressure in bars. Eq. (5) is cited because it provides a useful
check on the limiting slope of 7/w~s (Section 3.2) and might be useful for
preliminary estimates for multicomponent solutions at moderate concentra-
tions (Sections 2.3 and 3.5).
856 Leyendekkers

2.2. Limiting Viscosity Slope

Equation (1) may be written
~s = ~w,s exp [f(m)l
so that

am] L \ am ] + ~wls~ ] ] exp [Am)] (6)

and with
f ( m ) = affn + a2rn 2 + . . . (la)
in the limit as the concentration approaches zero,

amim-.o = \ am Ira-0 + Vwax = 7 / w [ l ~ ] m + o + al (7)

Since, from Eq. (3), (apJam)m-~o = Mhzl0 -a, where M is the molecular
weight of the salt, then, from Eqs. (4) or (5),
(&,Ti~/am)~._,o = Mh~ IO-3BL (S)
with ~Tn = Vw~/%. For Eq. (4) B~. is given by
BL = O tog (V~/~7o) + [D/2.303d*v~(1 -- d*v~,)] (9)

x _~o~b'J(~--1)J(d*-~-l)J

where D = (0.315/(B~ + 1), with

Br = 2671.8 + 19.454t - 0.27028t z + 9.798 • 10-~t 3 (bar)
0 ~< t ~< 45~ (10)
from the Tait equation(~3~; Vw is the specific volume of water at 1 bar. At
20~ BL = --0.393 • 10 -~ from Eq. (9), whereas from Eq. (5) BL is simply
given by the second coefficient, i.e., Bt, = -0.342 • 10 -~, which is in good
agreement with the value from the IAPS equation. The limiting viscosity slope
is therefore given by

with Bz given by Eq. (9).

2.3. Multicomponent Solutions

On the basis of results for other solution properties/14-16"19'2~ the vis-
cosity of a solution containing r salts would be given by
~v~ = ~7~'~exp [F(m)] (12)
Viscosity of Aqueous Electrolyte Solutions and the TTG Model 857

where

p' = p + ~ P~ (12a)

with i representing any of the salts, and

r(m) = ~f(mi) (12b)

with rn~ the concentration of the salt i in the mixture.

3. R E S U L T S

3.1. Fit of General Equation

Values of ~ o + 1)/~w were calculated for 20 salts from Eqs. (3) and (4).
Values of ~s/~Tw were taken from ref. 21. For sodium chloride the data of
Korosi and Fabuss (22) were also used. Values of In [(%/Vw)/(V~e § 1)/~w)], that
is, In ( % / ~ § 1)), divided by m, were then fitted (by least squares) to m. For
the majority of electrolytes only two parameters were needed. A third
parameter was required for the alkaline earths, potassium carbonate, and
lithium chloride. The values of these parameters are given in Table I.
In general, the derived equations fitted the data within the experimental
errors. The experimental error for pure water is 0.270 (4) and the errors for the
solutions are of the order of 0.3 to 0.5~o (based on a comparison of data from
various sources(21-2a)). At the highest concentrations the errors may be as
large as 2~o or more. The percentage deviations between ~s(exp.) and r/~(calc. )
are given as a function of rn in Fig. 1. For sodium chloride the data of ref. 21
are too high at concentrations above 4 m. This conclusion is based on a
comparison with the data of Korosi and Fabuss (KF) (22) and Kestin. (2a) The
extrapolated K F data were in good agreement with four other data sets at
20~ (average deviations 0.04~o, 0.35~o, 0.16~o, and 0.15~o; Table VII of
ref. 22) and were used to obtain the values of al and a2 shown in Table I.
These parameters give a better fit to the data of ref. 21 than those derived
directly from that data set. This is probably due to the " t o o - h i g h " values at
concentrations above 4 m.
The need for three parameters in the case of some electrolytes is possibly
a reflection of inconsistencies in the data, both the water data at high pressures
and the solution data.
The viscosity data were also fitted to an equation of the form
In (~/s/~Twis) = A m 112 + b'm + c'rn 2 + . . . (13)
858 Leyendekkers

TableI. The TTG Viscosity Coefficients at 20~ [ E q . (1) w i t h f ( m ) = aim +

a2m 2 + aam 3]

M~bs, 10aa2 Concentration a

Salt cm a 102al kg-mole- 1 103aa range, mole-kg- 1

HC1 23.0 5.1091 (5.1) ~ -0,37579 -- 0-16.8

LiC1 28.2 14.908 (14.1) -5.9235 0.40564 0-10.1
14.415 -2.0829 --
NaC1 30.6 9.1625 (10.6) 3.2530 -- 0-6.3
NaBr 34.6 5.2498 (4.9) 7.1228 -- 0-6.5
KC1 38.4 -0.91536 (-0.6) 4.9260 -- 0-4.3
KBr 42.5 -4.5560 (-6.4) 9.3825 -- 0-5.6
NaHCO3 36.5 22.108 -- 12.336 -- 0-0.8
MgC12 48 41.763 -- -21.049 4.9857 0-4.3
40.562 -0.0315 --
CaC12 52 29.094 (29.7) -4.5290 2.3967 0-6
28.240 8.1862 --
SrC12 52 30.451 (29.7) - 35.554 12.378 0-3.6
28.722 4.8528 --
BaC12 57 27.897 (27.3) -91,089 46.169 0-1.7
26.245 - 17.189
Na2COa 45 51.950 (49.6) 24.921 -- 0-1.7
K2CO8 60.6 33.327 (29.6) - 32.924 5.1024 0-4.5
32.448 - 14.049
K2CrO4 78 18.342 (18.1) -1.8519 -- 0-2.2
Na2SO4 56 41.604 (39.1) 23.765 -- 0-1.3
K2SO4 75 17.999 (20.9) 63.206 -- 0-0.7
(NH~)2SO4 78.9 18.548 (17.2) 1.6009 -- 0-4.5
MgSO4 44.4 64.479 (60.8) 19,292 -- 0-2.9
CuSO4 41.6 60.891 (62.8) 35.735 -- 0-1.4
ZnSO4 40.8 63.333 (63.4) 23.727 -- 0-1.2

D a t a f r o m ref. 21.
b B r a c k e t e d values are calculated f r o m Eq. (15) with M~b~ values f r o m c o l u m n 2.

since this will reduce to the Jones-Dole equation for very dilute solutions.
Values of A (25~ were calculated f r o m (~,2~

B*
A=
80(Iz~l + [z=l)2

o2o2 E o o l}
• ~ A~; ~ (A~ 1~2 + ~ - ~I~-~11 + ~]Zl/Z21) ~
with
B* = ~(Izd + Iz2l)(~lzlz~l/2) ~,2 x 60.19 (14)
Viscosity of Aqueous Electrolyte Solutions and the TTG Model 859

HC[ 2

1 .... LiCt 3

0 2 4 6 8 10 12 14 16

- - NaC[(o) 2

2 .... Nc~Cl(b) 2

1 /
.f
.,~ 0

-1

-2

i I [ [ f L i [ ] ~ I i p
0 1 2 3 4 5 6 7

__ ~4L~r 2
2

1
~ 7 ~ - ~ - - NaE3r
0 "'"....... ~:zj:,-~~ . . . . . . . Z..'-.S,-------- ~ . . . . . Z~ ~

-1

-2

I I i I I i 1 I J p
0 ] 2 3 4 5 6 7
m mot kcj -1

Fig. 1. Deviations of calculated values from the experimental data A = 100[~/s(exp.) -

n~(calc,)]/~/~(exp.). 2, 3 indicate degree of fit (see Table I). For NaC1: (a) data from ref. 22;
(b) data from ref. 21.

where z is the ionic charge, v is the number of moles o f ions from one mole
o f salt, A~ is the limiting ionic mobility, and A ~ = A~ + A~.
Values of [In (~/~wJs) - AmZ/2]/m were fitted to m by least squares.
While this gave fair results for a few electrolytes (e.g., 1:1 electrolytes had a
standard deviation around 0.5-1~o), the overall results were inferior to those
obtained with Eq. (1).
A number o f studies have shown ~2) that data in the range 0.0001 to 0.1
mole-liter -1 fit the J o n e s - D o l e equation to 0.01~o. However, it should be
noted that in very dilute solutions the measured values are o f the same order o f
magnitude or less than the experimental errors. For example, at 10 -5 m,
at 20~ the values o f ( ~ - ~ ) / ~ w for NaC1, KC1, and HC1 are 0.006,
0.005, and 0.002~o, respectively. This applies to most of the 1:1 electrolytes.
860 Leyendekkers

_ _ (NH,~)z.504 2

2 .... F~CO~ 3

-1

I [ l l p l r i 1
1 2 3 5

_ _ Nggt 2 3

2 - E~CL2 3

ss 0
-1
\
-2

i i i i I i i i
1 2 3 4 5
_ _ CaCCz

? 5rC[ 2

-1 I

_2

I 2 3 4 5 6
rn mo[ kg -I
Fig. 1. Continued.

More complex salts for which the corresponding values are higher (ca. 0.01-
0.0270 ) generally have larger experimental errors. In any case, very accurate
dilute-solution data fit Eq. (1) as well as they fit the Jones-Dole equation
(Table II). In addition, the coefficients derived using the data at high concentra-
tions give similar results, taking into account that the data sets (dilute to
concentrated and very dilute) were different (Table II).

3.2. The T T G P a r a m e t e r s al and a2

The parameter al was found to be a linear function of the T T G volume,
M~s, divided by the charge density, w, or ( 8 9 However, the slopes for
the halides and oxyanion salts were not the same and the value of al for HC1
did not lie on the halide line. An analysis of deviations from the halide line
showed that all the values of a~ could be summarized by the equation
Y = Ao + A 1 X std. dev. +0.018 (15)
Viscosity of Aqueous Electrolyte Solutions and the TTG Model 861

__ K2 S 0~, 2
? ...... NaHCO 3 2
--- No2SO4 2
1

-I

-2

i p i i i i i p t I
0.5 1 1.5 2 25 3

2 __ K~c~q
.... N~CO 3
1

-1

-2
L i i i

0 0.5 1 1.5 2 2,5 3

__ euSO 4
2 ....... ZnSO4
--- Mgso4
1
%
o
\
-1 tl / - -

-)

t I I I 1 P J 1 i i I

0 0.5 I 1.5 2 25
rn mo~ kg -1

Fig. 1. Continued,

with Y = a~ for the hatides and Y = a~ - a~ (HCI) for the oxyanions. The
value of X for the halides is given by Mr and for the oxyanions by
2Mr - (Mr The values of Ao and A~ are 0.5458 and
-0.014355 respectively. The Mr data for MgC12 and NaHCOa were not
used in fitting Eq. (15) as they were considered less reliable. The value of the
limiting conductivity A~ is a linear function of the TTG volume per unit
charge density (aa) so that an equation similar to (15) can be derived with A ~
replacing Mr This gave Ao and A~ as 0.8364 and -0.005903, respectively
(std. dev. _+0.022) taking A~ as 91 ~2-~-cm 2 for the best fit. The
values of al from Eq. (15) are given in Table I.
As can be seen from Table I the values of az are relatively insensitive to
the degree of fit. For each electrolyte the value of al is close to the corres-
ponding Jones-Dole coefficient BaDa-a) (see Section 3.3). This is to be
expected since the expansion of the exponential of Eq. (1) approximates
(1 + a~m) at low concentrations. The parameter al is a component of the
 OD
i,o

Table II. Fit of Eq. (1) to Very Dilute Solution Data at 20~

f(m) calculated

0.1 rn 0.01 m
Concentration
_+std. ~ range
a / t
Salt 1 a2 dev, 70 moles-kg- 1 Dil.b Conc.~ Dil.b Conc.c

HC1 0.04726 0.1509 0.01 0.0008 to 0.13 0.0062 0.0051 0.00051 0.00049
NaCI a 0.09893 - 0.0039 < 0.01 0.001 to 0.15 0.0098 0.0092 0.00099 0.00092
KC1 - - 0.00780 0.0218 < 0.01 0.001 to 0.15 -- 0.0006 -- 0.0009 -- 0.00008 -- 0.00009
MgCI2 0.46318 -0.3379 0,01 0.0025 to 0.15 0.0429 0.0416 0.0046 0.0042
K2SO~ 0.27486 -0.3262 0.01 0.0025 to 0.12 0.0243 0.0243 0.0027 0.0018
MgSO4 e 0.78742 -1.0113 0.04 0.0005 to 0.12 0.0686 0.0664 0.0078 0.0065

S t a n d a r d d e v i a t i o n o f 100 [(~s/~Tw)exp - (~J~w)o~lo]/(~s/~w)e~p; e x p e r i m e n t a l d a t a were i n t e r p o l a t e d u s i n g (~Ts/~w) = 1 + A m 112 + Brn +

Cm 2 with coefficients f r o m ref. 2; differences in c o n c e n t r a t i o n s m o l e s - l i t e r - 1 a n d m o l e s - k g - 1 were neglected.
b Dil. : a~ a n d a~ f r o m this table ( d a t a f r o m ref. 2).
e C o n c . : a~ a n d a2 f r o m Table I ( d a t a f r o m ref. 21).
a I n t e r p o l a t e d d a t a f r o m 25 a n d 15~ sets (ref. 2).
D a t a were at 18~ t e m p e r a t u r e c o r r e c t i o n w a s neglected.
r
r
e~
Viscosity of Aqueous Electrolyte Solutions and the TTG Model 863

limiting viscosity slope (Section 2.2) whereas BjD has no comparable relation-
ship. In this regard, the limiting coefficient Br~M~for the nuclear magnetic
relaxation (NMR) rate versus concentration ~2~ would be a more appropriate
comparison. This coefficient is compared with the viscosity limiting slope
in Section 3.3 where it is shown that Eq. (15) is compatible with a micro-
dynamic model developed for interpreting N M R data.
The parameter a2 is more sensitive to the errors and concentration
ranges of the data. Nevertheless, it is found to be quite simply related to
dM~b~/dt, the temperature differential of the TTG volume. The values of a2 for
the two-parameter fit can be summarized by

Y = 0.053 dM~b~
dt (16)

where Y depends on the charge type of electrolyte as follows: 1:1, Y =

-4(a2 - 0.002); 2:2, Y = a2; and 2:1 and 1:2, Y = a2 - 0.034. As outlined
previously <zs~dM~bJdt is equivalent to O(a~b~/at)~/amwhere ~bw is the volume
of the water in solution. The parameter az can thus be interpreted as arising
from changes in microdynamic structure due to increasing ion-ion interactions
at the higher concentrations.

3.3. Limiting Slope

Values of (1/~w)(~/~m)z were calculated from Eqs. (11) and (9) using
the values of al shown in Table I. The values are dominated by al at 20~
(Table III) because of the small value of BL. However, at 0~ the value of
Bz is -1.636 x 10 -4 [from (9)], which is nearly five times larger than the
value at 20~
The limiting values are approximately additive. For the univalent salts
and alkaline earths, estimates on this basis are to + 0.004. Deviations of
around 0.03 are found for the more complex salts (Table III).
Since the relative variation of the proton magnetic relaxation rate is of
the same order of magnitude as the relative variation of the viscosity, it is of
interest to compare the two limiting slopes (Table III). As pointed out by
Hertz(12> the values of B~Ma are not very precise; nevertheless the corres-
pondence with the viscosity slope is quite striking. This justifies a comparison
of the TTG results with the equations derived on the basis of a "microdynamic
model of nonoverlapping hydration spheres" given by Hertz, (~2>viz.

B,~,~ = ~+a~ + v - a s + ~ \~_g---6 - 1 +- 5-~.5 \~.oo - 1 (17)

where +, - , and zero represent the positive and negative ions and bulk
water, respectively; the second zero in the superscripts indicates the limiting
864 Leyendekkers

Table I I I . L i m i t i n g V i s c o s i t y Slope a t 2 0 ~

IO-aMhlBL (1/~?~)(d~7~/dm)z
Salt [ E q . (8)] [ E q . (7)] Bar, ~ Br~ b

HC1 - 0.0037 0.047 0.058 0.05

(0.065)
LiC1 - 0.0090 0.140 (0.143) 0.13
NaC1 - 0.0117 0.080 (0.079) 0.05
NaBr - 0.0093 0.043 -- 0.02
KC1 -0.0096 --0.019 --0.027 -0.02
(-0.014)
KBr - 0.0074 - 0.053 (- 0.049) - 0.05
NaHCO3 - 0,0102 0.211 -- 0.100
MgC12 - 0.0257 0.392 0.370 0.43
(0.371)
CaC12 - 0.0256 0.265 -- 0.25
SrC12 - 0.9246 0.280 -- 0.21
BaC12 - 0.0247 0.254 (0.207) 0,16
Na~CO3 - 0.0423 0.477 -- 0.37
K2CO3 - 0,0396 0.294 -- 0.23
K2CrO4 - 0.0296 0.154 (0.152) --
Na2SO4 - 0.0373 0.379 0.375 0.24
(0.382)
K2SO4 - 0.0344 0.146 0.170 0.10
(0.194)
(NH4)2SO4 - 0.0221 0.163 -- --
MgSO4 + 0.0384 0.606 0.597 0.57
CuSO4 - 0.0420 0.567 (0.540) --
ZnSO4 - 0.0406 0.593 -- --

Jones-Dole coefficient from ref. 2 (bracketed values are at 25~ others are at
20~
BrrM~ ~ [(1/T1)~,t~,] ~ I [d(1 ]T~)lntr~/dm]r, = o at 25~ [7'1 is the proton relaxation
rate (ref. 12)].

value as the concentration approaches zero, nh is the number of nearest-

neighbor water molecules to the ion (or the hydration, i.e., first coordination
number of the ion); v is defined in Eq. (14); % is the "effective" rotational
correlation time, which describes the reorientation motion in the first
hydration sphere of the ion, i.e., on the immediate surface of the ion. The
quantities ad- and ao derive from the effect of the ions on the bulk or fluid
water (water not within the hydration spheres) and are described by
[d('r~176176 = v+ a~ + v-ao (17a)

T o c o m p a r e t h e s e N M R results w i t h Eq. (15), Eq. (17) can be written

B N ~ = A' - Ai(~+nff + v-nff) (17b)

Viscosity of Aqueous Electrolyte Solutions and the TTG Model 865

with

A' = (v+a8~ + v - a g ) + ~. 55.5 roo0 + 55.5 r~176

and A[ = 0.018. The first term of A ' is comparable to the first term of (7)
which represents the effect of the ions on the bulk water. The second term of
A ' compares with Ao in (15), while A~ is of similar magnitude to A[. This
seems reasonable since the size and charge of the ions are critical determinants
of n~.
Since the change in the water correlation time produced by C1- is
negligible, (~2~and neglecting the ao terms, (17b) for chlorides approximates to
BNMR = v+n2('r~+~176176 - 0.018n~- (18)
If (17) is applied to the oxyanions and with the same assumptions as for
(18) we get
BNM~ -- BNM~(HCI) ~ 0.018(, + ~176176
) v +n +
- 0 . 0 1 8 ( v + n + + nh ~ - n g +) (19)

provided (~'~~o/~-o
0o)nh9 for H + and SO~- are of the same magnitude. Equation
(19) is similar in form to (I5) applied to oxyanions.
Since ~ o/~_oo,nh, and a0 values are not known independently, the above
comparisons can be only approximate. Nevertheless they do show that the
T T G and N M R models are compatible.
Finally, the value of (1/'qw)(~r/,~i,/Om)Lis related to the value of A [from
(14)], as shown in Fig. 2. The shearing forces acting on the ions (z>are smaller
and are in the opposite direction to the forces on the solvent and proportional
to them.

3.4. Pressure E f f e c t s

On the basis of the T T G model, the value o f f ( m ) of Eq. (1) should not
be very sensitive to pressure. Thus, neglecting any changes in f ( m ) , the
viscosity of the solution at pressure p is given by

,;(~>/~i> = ,jwi~J,1~-<'>
~-~i> = 7 7 ~+ ' > / ~ ~ + ~ (20)
Apart from the preliminary work of Kestin et al. ~23) there do not appear to be
any data for the viscosity of concentrated solutions under pressure at 20~
However, values of ~p>/~<1> for NaCI were calculated from Eqs. (3) and (4)
and compared with the interpolated experimental values. The agreement
ranged from 0.270 (to 100 bars) to I~o (around 300 bars). These results are
reasonable but no conclusions concerning the usefulness of (20) can be made
until more data are available.
866 Leyendel~kers

48 // ~/
44 f /
40 13o// o12 2~A"

"3 28
,-0
24
20 / "

! 8
4 / 6 ii
I
0 2 4 6 8 10 12 14 1 18 20 22 24 6

103 A
Fig. 2. A component of the TTG limiting viscosity slope [Eq. (7)] versus the Falkenhagen
slope [Eq. (14)1. (1) HC1; (2) LiC1; (3) NaC1; (4)NaBr; (5) KCI; (6) KBr; (7) NaHeOa;
(8) MgC12; (9) CaClz; (10) SrCI2; (11) BaCl2; (12) Na2CO3; (13) K2CO3; (14) K2CrO4;
(15) Na2SO4; (16) K2SO4; (17) (NH4)eSO4; (18) MgSO4; (19) CuSO4 ; (20) ZnSO4.

3.5. Multicomponent Solutions

The viscosities of three multicomponent systems (24~ were calculated
using (12) and the coefficients listed in Table I. The three-parameter equation
was used for MgC12. The experimental concentrations c were in moles-liter- 1
and were converted to rn (moles-kg -1) to conform to Eq. (12) using (13'~6~
ml = cl/dw[1 - 0.001(cl~vl + c24'v2)] (21)
neglecting any mixing effects on the volume (xs~and with the further approxi-
mation that 6v in a mixture at ionic strength I is equal to 6~ in a binary
solution at I. The subscripts refer to either of the salt pair, dw is the density of
water, and ~ is the apparent molal volume. The experimental and calculated
values of the viscosities are compared in Table IV. The results are considered
encouraging, since, judging by the deviations of the pure solutions, the
experimental errors are of the order of the deviations.

4. DISCUSSION
As for the other solution properties considered (density, refractive index,
and heat capacity)(13-16'19'2~ the TTG model gives a simple form of equation
over a very large concentration range and extending to multicomponent
Viscosity of Aqueous Electrolyte Solutions and the TTG Model 867

T a b l e IV. C o m p a r i s o n o f C a l c u l a t e d a n d E x p e r i m e n t a l Viscosities
o f T h r e e - C o m p o n e n t Systems ( W a t e r Plus Salt Pair) at 20~

~dnw
Concentrations
moles-kg- 1 (moles-liter- 1) ExpP calc2 [100(a - b)/a]%

NaC1 KC1
2.0844 (2) 0 (0) 1.2094 1.2133 -0.32
1,3629 (1.3) 0.7339 (0.7) 1.1271 1.1224 0.42
1,2593 (1.2) 0.8395 (0.8) 1.1165 1.1107 0.52
1.1971 (1.14) 0.9030 (0,86) 1.1093 1.1039 0,49
1.1555 (1.1) 0.9454 (0.9) 1.1051 1.0994 0.52
1.0516 (1.0) 1.0516 (1.0) 1,0944 1.0883 0.56
1.0100 (0.96) 1.0942 (1,04) 1.0901 1.0839 0.57
0.8432 (0.8) 1.2648 (1,2) 1.0734 1.0670 0.60
0.5289 (0.5) 1.5868 (1.5) 1.0428 1.0371 0.54
0 (0) 2.1303 (2) 0,9895 0.9925 -0.30

MgC12 KC1
1.0218 (1) 0 (0) 1.4854 1.4886 -0.22
0.7167 (0.7) 0.3071 (0.3) 1.3104 1.3188 -0.64
0.6148 (0.6) 0.4099 (0,4) 1.2556 1.2665 -0.87
0.5638 (0.55) 0.4613 (0.45) 1.2323 1.2412 -0.72
0.5332 (0.52) 0,4922 (0.48) 1.2172 1.2261 -0.73
0.5128 (0.5) 0.5128 (0.5) 1.2072 1.2162 -0.75
0.4924 (0.48) 0.5334 (0.52) 1.1979 1.2064 -0.71
0.4617 (0.45) 0.5644 (0.55) 1.1863 1.1917 -0,46
0 (0) 1.0315 (1) 0,9869 0.9898 -0.30

(NH4)2SO4 ZnSO4
0.5159 (0.5) 0 (0) 1.1052 1.0931 1.1
0.4627 (0.45) 0.0514 (0.05) 1.1263 1.1176 0.77
0.4100 (0.40) 0.1025 (0.10) 1.1494 1.1427 0.58
0.3315 (0.325) 0.1785 (0.175) t.1865 1.1815 0.42
0.2539 (0.250) 0.2539 (0.250) 1.2252 1.2217 0.29
0.2025 (0.200) 0.3038 (0.300) 1.2515 !.2493 0.17
0.1770 (0.175) 0.3287 (0.325) 1.2654 1.2634 0.16
0.1515 (0.150) 0.3534 (0.350) 1.2795 1.2777 0.14
0.1261 (0.125) 0.3782 (0.375) 1.2941 1.2921 0.16
0.1007 (0.100) 0.4029 (0.400) 1.3089 1.3067 0.17
0.0754 (0.075) 0.4275 (0.425) 1.3248 1.3214 0.25
0 (0) 0.5011 (0.5) 1.3886 1.3669 1,6

Experimental from Ref. 24.

b Calculated from Eqs. (12), (12a), (12b), and Table I (based on data from
ref. 21).
868 Leyendekkers

systems. The model is probably most compatible with interstitial or " h o l e "
type theories whereby the melting of a crystal occurs when a critical number
of holes is reached. (1,25~The solid in solution and the water are thus character-
ized by configurational holes. The effect of the solute on the water (the effect
of the charge, shape, and, in particular, the size of each ion) is to cause a
change in the molecular configuration. This may be a net deformation of
coordination bonds (~ or a decrease in vacant holes or some other change.
However, whatever the actual mechanism, the effect is to allow a molecule to
start its diffusive motion in the bulk solution, and this net configurational
change produces a change in volume. This is the same result as achieved by a
corresponding increase in pressure (in both cases, at low temperatures and
pressures, this change is negative).
Equation (1) is compatible with the Eyring theory, ~1~and it is of note also
that the T T G equation has a similar form to the equation derived from the
Othmer rule, ~22>viz.
log (%/~7~o+ 1)) = A~ = fl(m) (22)
where Bo = f2(m). Both A; and Bo are independent of temperature. While
Eq. (22) has been found very useful as a correlating function, (2~ it has also
been shown to have certain deficiencies.(23~ The T T G equation is expected
to be superior since it is based on a model which has been successfully applied
to other solution properties and has more flexibility (less constraints) than
Eq. (22). In addition, Eq. (1) extends to zero concentrations.
The correlations of the T T G parameters are consistent with the previous
results for other solution properties. (la-16,19'2~ The limiting relative viscosity
slope is seen to be made up of three terms: (1) the "volume change" effect
given by the Pe function, (2) the constant term A~, and (3) the volume-to-
charge ratio term. The first term is negative at low temperatures (0-30~
when pressures are low (e.g., 1-800 bars at 20~ The third term is also
negative. Thus, if these two terms together are dominant over the second, the
limiting value is negative. The second term is positive and from comparison
with the N M R results appears to be related to the relative microdynamics
(reorientational motions) of the water molecules that are adjacent to the ions.
This breakdown of the limiting slope (which is close in magnitude to BN~g)
explains why large univalent ions have negative BN~s~ values and higher
charged ions tend to have positive slopes (unless they are very large). Since the
first term is more negative at 0~ this indicates that d(a~ + a~)/dt is positive,
which agrees with the N M R results.
The first term of the slope, (1/r/~)(O'q,~Jam)L, is proportional to but
opposite in sign to the shearing forces acting on the ions as calculated on the
basis of the Debye-Hiickel type theory of Falkenhagen et alY '2~ As shown by
Eq. (14) such forces are a function of the limiting ionic mobilities and charges.
Viscosity of Aqueous Electrolyte Solutions and the TTG Model 869

In addition, al is also a function of the limiting mobilities and charge densities

(Section 3.2). Thus, the TTG limiting viscosity slope can be described in
terms of these ionic properties.

REFERENCES
1. T. Erdey-Gruz, Transport Phenomena in Aqueous Solutions (Wiley, New York, 1974).
2. R. H. Stokes and R. Mills, Viscosity of Electrolytes and Related Properties (Oxford
University Press, London, 1965).
3. R. L. Kay, in Water. A Comprehensive Treatise, Vol. 3, F. Franks, ed. (Plenum Press,
New York, 1973), p. 173.
4. G. S. Kell, in Water, A Comprehensive Treatise, Vol. 1, F. Franks, ed. (Plenum Press,
New York, 1972), p. 404.
5. T. Satch, J. Phys. Soe. Jpn. 15, 1134 (1960).
6. G . Ebert and J. Wendorff, Ber. Bunsenges. Phys. Chem. 75, 82 (1971).
7. C. V. Suryanarayana and V. K. Venkatesan, Monatsh. Chem. 90, 36 (1959).
8. D. W. James and R. L. Frost, J. Chem. Soc. Faraday Trans. 1, 74, 583 (1978).
9. D. E. Goldsack and R. C. Franchetto, Can. J. Chem. 56, 1442 (1978).
10. C. A. Angell and R. D. Bressel, J. Phys. Chem. 76, 3244 (1972).
11. G. Maisano, P. Migliardo, and F. Wanderlingh, J. Chem. Phys. 68, 5594 (1978).
12. H. G. Hertz, in Water. A Comprehensive Treatise, Vol. 3, F. Franks, ed. (Plenum
Press, New York, 1973), p. 373.
13. J. V. Leyendekkers, Thermodynamics of Seawater as a Multicomponent Electrolyte
Solution, Part I (Marcel Dekker, New York, 1976), p. 408.
14. J. V. Leyendekkers and R. J. Hunter, J. Phys. Chem. 81, 1657 (1977).
15. J. V. Leyendekkers, J. Chem. Soc. Faraday Trans. 1, in press (1979).
16. J. V. Leyendekkers and R. J. Hunter, J. Chem. Eng. Data 22, 427 (1977).
17. International Association for the Properties of Steam Release on Dynamic Viscosity
of Water Substances, Sept. 1975. Mech. Eng., July 1976, p. 79.
18. E. M. Stanely and R. C. Batten, J. Phys. Chem. 73, 1187 (1969).
19. J. V. Leyendekkers and R. J. Hunter, Mar. Chem. 6, 71 (1978).
20. J. V. Leyendekkers, Mar. Chem., submitted.
21. A. V. Wolf, M. G. Brown, and P. G. Prentiss, Concentrative Properties of Aqueous
Solutions, Handbook of Chemistry and Physics (Chemical Rubber Publishing Com-
pany, Cleveland, Ohio, 1973-1974).
22. A. Korosi and B. M. Fabuss, or. Chem. Eng. Data 13, 548 (1968).
23. J. Kestin, H. Ezzat Khalifa, Sung-Tack Ro, and W. A. Wakeham, J. Chem. Eng.
Data 22, 207 (1977).
24. I. Tollert, Z. Phys. Chem. Abt. A 184, 150 (1939).
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New York, 1972), pp. 17, 537.