Viscosity of associated liquids

R. C. MAKHIJA AND R. A. STAIRS'

Departme~if of Chemistry, Trent University, Peterborough, Ontario
Received November 13, 1969
Viscosity data for ammonia, methylamine, and 1,2-diaminopropane have been obtained in the tem-
perature ranges - 65 to - 35, - 65 to - 10, and - 35 to + 50 "C, respectively, using an Ubbelohde
viscometer. The results were compared with existing data, and all the data were fitted to the Fulcher
(Tammann-Hesse) equation by the method of least squares. The significance of the values of To in this
equation for these and other associated liquids was considered.
Les valeurs de viscosite pour I'ammoniac liquide, la methylamine et le 1,2-diaminopropane ont kt6
obtenues dans les intervalles de temperature suivants: -65 a -35, -65 a - 10 et -35 a +50 "C,
respectivement, utilisant un viscosimtttre Ubbelohde. Les r6sultats ont et econi par~s aux valeurs existantes,
et les constantes de I'dquation Fulcher (Tammann-Hesse) ont Ct C trouvCes par la methode des moindres
carres. La signification des valeurs de To dans cette Cquation a etC considerCe pour ces liquides contenant
des liaisons hydrogttne et d'autres composes similaires.
Canadian Journal of Chemistry, 48, 1214 (1970)
I n the search for a simple equation to express
the dependence of the viscosity, q, of liquids on
absolute temperature, T, over an extended range,
the equation apparently first proposed by Fulcher
(1)
and used by Tammann and Hesse (2), Prasad (3),
Gut ~uann and Simmons (4, 5), and recently by
Miller (6), has been somewhat neglected. Part of
this neglect may be due t o the fact that it is not
simply explicable in terms of an "activation
energy for flow."
Gutmann and Simmons showed that eq. [l ] is
obtained if the activation energy, Eo, varies with
temperature as Eo/(a + b/ T), where a and b are
constants. This, however, is an unsatisfying form,
hard to relate t o molecular or thermodynamic
concepts. They also succeeded in deriving the
equation from what they described as a quantum
form of the Maxwell-Boltzmann distribution
law, attributingthe deviation oft he viscosity from
the Andrade equation (7)
Gutmann and Simmons have derived normal
equations for least-squares fitting of eq. [ l ] t o
data, but we prefer eqs. [3] for this purpose, as
they throw less undue weight on the higher-
temperature points.
where y = log q, T = absolute temperature, D =
B - AT,, and A, B, and To are the constants i n
eq. [l l .
Using a computer, we have fitted the Fulcher
equation t o data for the viscosity of several
oxygen- and nitrogen-containing associated
liquids. The results are listed in Table 3. Dat a for
the alcohols, glycol, and glycerol were obtained
from various literature sources (8-10). Dat a for
ammonia in the literature were included with our
own, and our own data were used for methyl-
amine and 1,2-diaminopropane.
where A' is a constant and R is the gas constant,
Experimental
t o other causes than inconstancy of E. It must be
The -/iscosities of liqtiid ammonia, methylamine, and
admitted that the theoretical justification for eq.
1,2-diaminopropane were measured by capillary flow,
1 is uncertain, but it fit the data for diverse
using Ubbelohde (suspended-level) viscometers, adapted
liquids well, and is not too difficult to apply. for use in a closed system as shown in Fig. 1. The design
permits introduction of sample without admission of air,
IT^^^^^^^^^ address L:ntil ~~~~~t 1, 1970: c/o Depart-
by distillation or through the side-arm, and makes it un-
nient of Chemistry, University of California, Berkeley,
necessary to know the volume of the liquid; the working
Calif. 94720. volume being that between the upper meniscus (moving
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MAKHIJA AND STAIRS: VISCOSITY OF ASSOCIATED LIQUIDS 1215
to Vocuum Li ne
The gas used to move the liquids in the viscometer was
hydrogen (Matheson, electrolytic) purified by passage
over a "Deoxo" catalytic purifier and phosphorus
pentoxide.
Temperature control above 0 "C was achieved by a
water-bath thermostat of conventional design, and tem-
peratures in this range were measured by a mercury-in-
glass thermometer, graduated to 1/10 degree, and cor-
rected at ice point. Temperature control at lower tem-
peratures was achieved by a thermostat of special design.
(for Breaker- Methanol contained in a large Dewar vessel was circu-
Adaptor)
lated through a copper coil, immersed in Dry Ice -
V'4/35
acetone in another vessel, by a centrifugal pump which
was controlled by a YSI thermistor controller. By this
means, the temperature could be controlled within 0.1
degree at any point down to about - 70 "C.
Bath Liq.
In the present work, time was measured manually,
Level
using an electrical stop watch.
The method employed yields the kinematic viscosity
v = q/p, where q is viscosity and p the density of the
liquid. The required densities for ammonia were taken
from Johnson and Martens (1 1, 12), and for methylamine
from Felsing and Thomas (13). Densities for 1,2-diamino-
propane not being available, they were measured by
means of a dilatometer fitted with a ground joint for
attachment to the vacuum line and a stopcock. I t was
filled by distillation under vacuum with the diamine,
purified as described. With the stopcock closed, it was
removed from the line, weighed, and the position of the
meniscus in the "Trubore" neck observed with a cath-
etometer at different temperatures. I t was calibrated using
distilled water.
The observed times were related to viscosity through
the equation
FIG. 1. Viscometer for use with air-sensitive liquids
and solutions.
v = q/ p = At - B/t
between the marks at A and B) and the bottom of the
capillary at D. The viscorneters were calibrated against
water in the temperature range 0-50 "C, using data for
the viscosity and density of water from the Handbook of
Chemistry and Physics (10).
Ammonia (Matheson) was distilled from the cylinder
onto sodium in the vacuum line. After allowing a portion
to escape, together with any hydrogen formed, a further
portion was subjected to two bulb-to-bulb fractionations,
and finally distilled into the viscometer. Methylamine
was similarly treated, except that lithium replaced sodium,
and 24 h were allowed for reaction with water or any
other reducible impurities.
1,2-diaminopropane (various sources, including B.D.H.,
Ana Chimia, and BASF) was purified by refluxing over-
night with potassium hydroxide, followed by distillation
under nitrogen over sodium wire. It was again distilled
and a middle fraction of boiling range 117.5-1 18.5 "C
was retained. This distilled product was finally distilled
under vacuum into a number of break-seal vials, which
were then sealed off from the line where indicated in Fig.
2a. The contents of a vial were transferred to the vis-
cometer without access of air or entry of broken glass by
means of the adaptor with fritted disk, illustrated in
Fig. 26.
where A and Bar e constants which we did not attempt to
calculate absolutely, but obtained, by calibration with
water and n-butanol at a number of temperatures, from
the intercept and slope of a plot of v/t vs. l / t z. The
values for the various viscometers used are listed in
Table 1.
Seal
.Magneti c
"hammer"
( a ( b )
FIG. 2. (a) Break-seal vial. (6) Breaker-adaptor.
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CANADIAN JOURNAL OF CHEMISTRY. VOL. 48, 1970
TABLE 1
value 0.2543 cP at - 33.5 "C found by Elsey (14).
Calibration of viscometers
Fitzgerald's value at this temperature appears to
be nearly 5 % high (15). A large graph of log q vs.
Viscometer Used with A lo3 BIA reciprocal temperature, on which all the available
I Ammonia 1.288 data were plotted, made it apparent that the data
11 Ammonia 3.128 4.77 of Pinevich (16) are inconsistent with the others,
I11 Methylamine 2.69
IV 1,2~Diaminopropane ::::: (negligible) being too high at his higher temperatures (30,
60 "C) by as much as 25 %. The data of Carmichael
Because of the disparity between the temperatures of
calibration and measurement, the effect of thermal ex-
pansion of the Pyrex glass of the viscometers was cal-
culated, and found t o be negligible.
Results and Discussion
The values of the viscosity of ammonia ob-
tained in this work, together with some earlier
measurements made using the same method by
Stairs (unpublished), and our results for viscosity
of methylamine and viscosity and density of 1,2-
diaminopropane are collected in Table 2. The
results for ammonia agree within 0.33% with
those in the Handbook of Chemistry and Physics
(lo), and support, by a short extrapolation, the
and Sage (17) tend towards low values at higher
temperatures (70, 100 "C), but this seems to be a
real effect, due to the increasing specific volume
of ammonia under its own vapor pressure at these
temperatures. These two sets of data were accord-
ingly excluded from those used to fit the Fulcher
equation, which was not expected to be valid
under conditions of grossly-varying specific
volume.
The only available data for methylamine were
those of Fitzgerald (1 5), who gives q as 0.2364 cP
at 0 "C, and of Berns et al. (18), who give values
differing from that of Fitzgerald at 0 "C by 16 %.
Our measurements agree with Fitzgerald at the
highest temperature and with Berns et al. at the
TABLE 2
(a) Viscosity of ammonia and methylamine at various temperatures
Ammonia Methylamine
t ("C) rl (cP) t ("C) rl (cP) t r c ) rl (cP)
(b) Viscosity and density of 1,2-diaminopropane at various temperatures
t Cc) rl (cP) P (glml) t Cc) rl (cP) P (g/ml)
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MAKHIJA AND STAIRS: VISCOSITY OF ASSOCIATED LIQUIDS 1217
lowest. There seemed no way ofchoosing between
them, so we used our results only to fit the Fulcher
equation. The only data for 1 ,2-diaminopropane
were estimates found in industrial bulletins (19,
20), with which our measurements appear to
agree. We again fitted the equation to our data
alone.
TABLE 3
Viscosity of methylamine by
Berns et al. (18)
On examining the Fulcher equation constants
in Table 4 for trends of possible significance, we
noted that the quantity To (written as - C by
some authors) is largest for those liquids in which
very extensive hydrogen bonding is possible,
leading to possible formation of chains or net-
works. This is apparent in the sequence of water
and the normal alcohols, where, as the hindrance
to polymerization through hydrogen bonding due
t o the bulk of the alkyl group increases, To tends
rapidly to small values. In the sequence of com-
pounds H(CHOH),H, however, the value of To
tends to maintain the value (about - 120 to - 140)
characteristic of water. At these temperatures, the
quantity RT is about 1/10 of the energy of disso-
ciation of a hydrogen bond between two oxygens
(about 3 kcal/mole), and it appears that the
liquids at these and lower temperatures are, in
effect, brittle glasses. (The glass transition tem-
perature, where it can be observed, seems to occur
a few degrees above To. See, for example, refs. 2
and 21 .)
The tendency towards extensive polymerization
is less apparent in ammonia, the value of To being
less than half that of water, but in the diamine,
the two hydrogen-bonding groups restore the
tendency to polymerize. That methylamine shows
a larger value of To than does methanol is puzzling,
but the range of the measurements is not great
TABLE 4
Fit of viscosity of associated liquids to the Fulcher equation log q = A + B/(T - To)
Constants in eq. [ I ]
Liquid A B To Percent error of fit* Range ("C)
Ammonia - 1 .7520 218.76 50.701 0.76 -69 to +40
Methylamine - 1 .3634 126.389 102.886 0.32 -70 to -10
1,2-Diaminopropane - 1 .0755 165.754 166.751 1.10 -35 to +50
Methanol -1.6807 354.876 48.585 2.05 -98.3 to +50
Water - 1 .5668 230.298 146.797 0.51 - 10 to +I60
Ethanol - 2.4401 774.414 -15.249 2.66 -98.11 to +70
Glycerin -2.8834 997.586 128.481 4.50 -42 to +30
Ethylene glycol - 1.5923 438.064 141.617 0.18 +20 t o+100
n-Propanol - 2.4907 725.903 37.474 1.10 0 to +70
n-Butanol -3.0037 1033.306 - 4.3828 0.80 -50.9 to +I 00
and the extrapolation is long, so the value of To
The authors wish to thank DuPont of Canada,
for methylamine may be in error.
Limited, for the gift of a quantity of 1,2-diaminopropane.
The significance of the other constants remains 1. G. s. FULCHER. J. Amer. Cerarn. Soc. 8,339 (1925).
obscure. There is a tendency for B to increase with
2. G. TAMMANNand W. HESSE. Z. Anorg. Chem.
156, 245 (1926).
increasing molecular weight, but its significance
3. B. PRASAD. Phil. Mag. 16, 263 (1933).
as proportional to an activation energy, which 4. F. GUTMANN and L. M. SIMMONS. Aust. J. Sci. 13,
109 (1951).
be in
with this observation, is
5. F. GUTMANN and L, M. S I ~ ~ ~ ~ ~ . J. APpl. PhyS.
obscure, as was remarked above. The significance
23,977 (1952).
of A, which in the Andrade equation can be 6. A. A. MILLER. Science, 163, 1325 (1969).
7. E. N. DA C. ANDRADE. Nature, 125 (1930).
as a "jump fact0r", is
8. International critical tables. Vols. 5 and 7, McGraw-
obscure. Hill Book Co., Inc. 1930.
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1218 CANADIAN JOURNAL OF C
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