Rheol. Acta 19, 660-667 (1980) 1980 Dr.

Dietrich Steinkopff Verlag, Darmstadt ISSN 0035-4511 / ASTM-Coden: RHEAAK

Fritz-Haber-lnstitut der Max-Planck-Gesellschaft, Berlin

Exact calibration of KPG-Ubbelohde-viscometers*)

J. M e l s h e i m e r and N. E. z a l t a y
With 2 figures and 9 tables (Received April 19, 1980)

1. Introduction
If flow times are brief, capillary viscosity measurements on low-viscosity fluids and solutions and the evaluation o f these taust be p e r f o r m e d with particular exactness. Especially in the determination o f absolute viscosity, targe-scale errors m a y occur due to inexact H a g e n b a c h - C o u e t t e correction, but it m a y also h a p p e n that the specific viscosity, necessary for calculation o f the viscosity n u m b e r (limiting viscosity number) is incorrect. Viscometers must be calibrated exactly, in order to do justice to the requirement for times and viscosities which have been corrected within the scope o f the applicable measuring accuracy. However, correctly determining the H a g e n b a c h - C o u e t t e error for such viscometers is difficult. It is well known, this error increases as flow times decrease. One further difficulty consists o f the fact that the H a g e n b a c h - C o u e t t e correction coefficient m is no constant but, as has already been shown b y Cannon et al. (1), is a function o f the flow rate or the Reynolds number. Moreover, the H a g e n b a c h - C o u e t t e error also depends on the shape o f the capillary inlet or outlet. Using the example o f K P G - U b b e l o h d e viscometers, this paper illustrates h o w to p e r f o r m exact calibration o f these viscometers.

regulation with a resistance thermometer Pt 100 in accordance with DIN 43760 as measurement sensor, were used for tempering. In order to obtain an even better temperature constancy, the thermostats were enveloped in an expanded polystyrene cover with a diameter of approximately 5 cm, leaving about 2 cm air gap to the thermostats. Temperatures were measured with a Hewlett and Packard quartz thermometer and the pertinent temperature sensitive dement Pt 100 was p!aced near to the working capillary of the viscometer in a glass tube filled with the test fluid. Water served as the thermostat fluid for viscometer calibration. It was not necessary to remove the viscometers from their measuring stands to fill them with the test fluid, as the lower reservoir of the viscometer was linked by means of a teflon hose to filling flask incorporating a D 4 glass frit. The fluid was conveyed to the viscometer under Nitrogen (NE) pressure and, after the completion of measurements, sucked into a suction flask with the aid of a water jet pump. This guaranteed clean fluid measurements. In order to permit correct measurements also at higher temperatures ( > 60 C), one part of the viscometer tube was linked to a so-called compensations reservoir (b) containing a few milliliters of the test fluid. This excluded the risk of impairing the measurements by the thermostat fluid vapor. Figure I schematically illustrates the viscosity measurement system without the basic unit and selector module with the supplementary components fitted by ourselves.

3. Calibration of the KPG-Ubbelohdeviscometers

2. Apparatus
The authors used the automatic viscosity measurement system from Schott, which incorporates light barriers for time measurement and a selector module for six viscometers. Transparent thermostats CT from Schott for two and six viscometers, which attain a temperature constancy better than 0.01C by means of proportional *) Part of a thesis of N.E..
643

3.1. Calibration fluid measurement

Tridistilled water with a conductivity o f 1.10-6 siemens/cm was used as the calibration fluid. The viscometer was previously flushed with N 2 and the water (about 17 tal) was conveyed to the lower reservoir (f) o f the viscometer under N 2 pressure f r o m the filling flask (c). In order to remove c a r b o n dioxide (CO2), a soda-asbestos absorber f r o m Merck (granulated, at least 50%

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661

e f

Fig. 1. Composite schematic of viscometer system. (a) - lower and upper vent tubes, (b) - compensation reservoir, (c) - filling flask with D4 glass frit, (d) three-way valve, (e) - thermostate fluid, (f) - lower reservoir, (g) - sucking flask, (h) - measuring stand, (i) - timing bulb, (k) - light barriers sense, (1) - working capillary, (m) - teflon hose, (n) temperature sensitive element Pt 100, (o) - air gap of the thermostate, (p) - expanded polystyrene cover

a b s o r p t i o n ) is c o n n e c t e d b e t w e e n the lower a n d u p p e r vent tubes o f the v i s c o m e t e r (a), t h r o u g h w h i c h the fluid is s u c k e d u p in t h e v i s c o m e t e r o r t h r o u g h which the v i s c o m e t e r can be a i r a t e d , a n d the basic unit o f the A V S viscosity m e a s u r e m e n t system. W a t e r m e a s u r e m e n t s c a r r i e d o u t over a l o n g p e r i o d o f t i m e w i t h o u t the a b s o r b e r resulted in decreasing flow times ( r e f e r r e d to b e l o w as time(s)) within the d e c i s e c o n d range. Five S c h o t t - K P G - U b b e l o h d e - v i s c o m e t e r s D I N 51562 with c a p i l l a r y n u m b e r 0c ( D I to D V ) a n d t w o S c h o t t - K P G U b b e l o h d e - v i s c o m e t e r s A S T M D2515 with c a p i l l a r y n u m b e r 0c ( A I a n d A I I ) were c a l i b r a t CO 2

ed. T h e w a t e r m e a s u r e m e n t s were p e r f o r m e d in stacks o f f o u r degrees f r o m 17 C to 73 C with the v i s c o m e t e r s D l , D I I , D I I I , A I a n d A I , a n d f r o m 17 C to 88 C with the v i s c o m e t e r s D I V a n d D V . O n e series o f m e a s u r e m e n t with the v a r i o u s v i s c o m e t e r s lasted f o r a b o u t 2 days; u p to 4 series o f m e a s u r e m e n t s were c a r r i e d o u t with new filling o f w a t e r each time. D e p e n d i n g on the d u r a t i o n o f one m e a s u r e m e n t , u p to three t e m p e r a t u r e s per t i m e value were registered b y a p r i n t e r . T a b l e 1 shows a n excerpt f r o m a m e a s u r e m e n t r e c o r d . W h e n c a l i b r a t i n g viscom e t e r D I , the t e m p e r a t u r e was set p a r t i c u l a r l y c a r e f u l l y in o r d e r to o b t a i n the s a m e t e m p e r a t u r e s as the t e m p e r a t u r e s o f the first series o f m e a s u r e m e n t s in r e p e a t i n g . T h e m e a s u r e m e n t d a t a listed in t a b l e 2 clearly illustrate the g o o d r e p r o d u c i b i l i t y o b t a i n e d d u r i n g these m e a s u r e m e n t s . E a c h m e a s u r e m e n t p r o c e d u r e at one t e m p e r a t u r e was r e p e a t e d o n average 10 times for the t i m e a n d 25 times for the t e m p e r a t u r e . T a b l e 2 shows the resulting fime a n d t e m p e r a t u r e uncertainties f o r viscom e t e r D I.

3.2. Calculation o f viscometer constants

W i t h the a i d o f the e q u a t i o n v = K - M - t - L - (1 +

Mu)5/2/tn

[1]

the v i s c o m e t e r c o n s t a n t s K, L a n d n were c a l c u l a t e d (2). I n these e q u a t i o n , v, t a n d M ( M , Mu) are the k i n e m a t i c viscosity, the t i m e a n d c o r r e c t i o n factors, respectively, whereby

M=

1 + Ma + Mu

[la]

Table 1. Excerpt from the measurement record for temperature and time measurements of the KPGUbbelohde-viscosimeter DII. Temperatures and times were continuously measured from top to bottom. (3rd series of measurements) Temperature C 33.011 33.011 33.011 33.011 33.012 33.011 33.012 33.011 33.011 33.012 33.011 33.011 33.011 33.011 33.013 33.013 33.013 33.014 33.014 33.014 33.014 33.013 Time s 280.56 280.56 280.56 280.56 280.55 280.55 280.54 Temperature C 37.001 37.001 37.001 37.001 37.001 37.001 37.002 37.001 37.001 37.001 37.001 37.001 37.002 37.001 37.002 37.001 37.002 37.002 Time s 259.76 259.76 259.76 259.77 259.76 259.76 259.76 259.76 259.75 Temperature C 41.025 41.024 41.024 41.027 41.026 41.028 41.029 41.028 41.026 41.026 41.025 41.021 41.019 41.019 41.022 41.024 41.026 41.026 41.024 41.029 41.024 41.023 41.024 41.024 41.025 41.027 41.027 41.028 41.031 41.027 41.028 41.022 41.022 Time s 241.43 241.43 241.44 241.42 241.43 241.45 241.44 241.45 241.43 241.43 241.43 241.43 241.44

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Table 2. Temperature-time measurement data from various series of measurements with the KPG-Ubbelohdeviscometer D I Series of measurements 1 3 1 3 1 2 3 1 3 1 3 1 3 4 Temperature C 17.085 + .002 17.080 + .004 24.990 +_ .002 24.990 _+ .000 29.017 +_ .001 29.018 _+ .004 29.016 _+ .002 33.015 + .001 33.014 + .001 41.017 + .003 41.017 _+ .001 45.058 + .002 45.058 _+ .002 45.051 _+ .003 Time s 351.89 _+ .02 351.91 + .02 291.93 + .02 291.96 + .02 267.83 _+ .01 267.74 _+ .02 267.83 +_ .02 247.08 + .01 247.07 + .01 212.81 + .01 212.82 _+ .02 198.68 + .00 198.67 + .01 198.67 _+ .02 Series of measurements 1 3 4 1 3 1 3 4 1 3 1 3 1 3 Temperature C 49.043 + .002 49.043 + .000 49.050 _+ .003 53.020 _+ .003 53.020 + .002 60.985 + .002 60.993 _+ .003 60.992 + .003 64.953 _+ .001 64.950 + .005 68.999 + .003 68.999 + .004 72.992 +_ .004 72.993 + .004 Time s 186.35 _+ .02 186.34 _+ .00 186.28 _+ .02 175.38 _+ .01 175.38 _+ .02 156.73 _+ .01 156.75 + .02 156.70 _+ .02 148.78 + .01 148.78 _+ .01 141.47 + .01 141.48 _+ .03 135.01 + .02 135.03 + .03

with

M a = -dL/d
and

[lb]

the r u n with t h e m e a n linear coefficient o f t h e r m a l e x p a n s i o n for the v i s c o m e t e r glass = 3.25 10 6 ( d e g - l )

M u = ~ ( t 9 - ~qc).

[lc1

a n d the c a l i b r a t i o n t e m p e r a t u r e
~ = 1 7 . 0 o c .

V a r i o u s a u t h o r s gave eq. [1] either w i t h o u t the c o r r e c t i o n factors (3, 4) o r t h e y o n l y used it with the c o r r e c t i o n f a c t o r M a (5, 6) o r with f u r t h e r c o r r e c t i o n f a c t o r s ( c o r r e c t i o n for the surface tension effect (7) a n d c o r r e c t i o n f o r the t e m p e r a t u r e o f filling (8)). W i t h the d e n s i t y o f the m o i s t air d L a n d the w a t e r d w, eq. [lb] represents the air c o l u m n c o r r e c t i o n f a c t o r which was d e t e r m i n e d with the f o l l o w i n g e q u a t i o n s t a k e n f r o m the l i t e r a t u r e (9) d r = 6.1926 . p / ( 2 7 3 . 1 6 + ~q) and d W = (1 - ( t ~ - 3.9863)2/508929.2 (t9 + 288.9414)/(t9 + 68.12963)) 0.999973. [2b] [2a]

T h e surface t e n s i o n effect in the c a l i b r a t i o n o f U b b e l o h d e - v i s c o m e t e r p e r f o r m e d with the a i d o f a fluid is negligible; t h e r e f o r e , it is n o t t a k e n into c o n s i d e r a t i o n . W i t h e q u a l l y w e i g h t e d m e a s u r e m e n t d a t a , all calculations o f m o s t p r o b a b l e values were p e r f o r m e d o n a D E C 10 with a p r o g r a m w r i t t e n in F O R T R A N 10 b a s e d o n v a r i o u s S U B R O U T I N E S w r i t t e n b y Bevington (10). T h e viscosity d a t a at the m e a s u r e m e n t t e m p e r a t u r e s , necessary f o r e v a l u a t i o n o f eq. [1], were p e r f o r m e d in a t e m p e r a t u r e r a n g e f r o m 15 - 17 C with the so-called H Y B R I D e q u a t i o n (11): r/ = A exp [ B / ( T - To) + C / T l [3]

I n eqs. [2a] a n d [2b], p is the air pressure in pascals a n d t~ is the t e m p e r a t u r e in C. Eq. [lc] specifies the c o r r e c t i o n for the t e m p e r a t u r e o f

with highly precise d a t a f r o m Korson et al. (5). In eq. [3] I1 signifies the d y n a m i c viscosity, T t h e a b s o l u t e t e m p e r a t u r e a n d t h e p a r a m e t e r s A , B, T o a n d C the t e m p e r a t u r e coefficients o f t h e viscosity. T h e p a r a m e t e r s o f eq. [3] necessary ,

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663

Table 3. Viscometer constants K, L, n; standard errors of the coefficients and standard deviations, in accordance with eq. [1], for the KPG-Ubbelohde-viscometer D1 Series of
measurements

K - 10 3
cm 2 . s_2

S.E. Coef.
K 10 3 cm 2

L
. S n-I

S.E. Coef.
L

S.E. Coef.
n

st. dev.

cm2. s 2 1 2 3 3.0851 3,0864 3.0851 0.0015 0.0005 0.0013 15.4 12.5 13.8

cm2. s_l 5.8 1.5 4.2 1.37 0.08 1.32 0.02 1.35 0.06
2.46. 10 -4

7.57 10 -5
1.92. 10 -4

Table 4. Viscometer constants K, L, n (average from several series of measurements), and standard errors of the coefficients, in accordance with eq. [1], for KPG-Ubbelohde-viscometers Viscometer K- 103
cm 2 . s-2

S.E. Coef. K 10 3
cm . s-2

L
cm 2 . Sn-1

S.E. Coef. L
cm 2 . sn-I

S.E. Coef. n

D D D D D A A

I II III IV V I II

3.0855 2.6850 2.6620 2.917 3.0570 2.480 2.6559

0.0015 0.0017 0.0013 0.005 0.0022 0.004 0.0016

13.9 75.0 4.4 6.6 23.0 108.0 22.0

5.8 29 1.2 1.0 5.3 44 10

1.35 1.74 1.16 1.09 1.45 1.79 1.57

0.08 0.08 0.05 0.04 0.04 0.09 0.09

for the calculation of most probable values are listed in table 8. From eq. [2b], the required densities for the measurement temperatures were calculated to an accuracy of six digits after the decimal point, which is permissible for water. The dynamic viscosities issuing from eq. [3] and the water densities calculated at the measurement temperatures result in kinematic viscosities which can be given with an accuracy to four digits after the decimal point, thanks to the high precise water data (see table 7). Table 3 lists the constants of the viscometer D I with their standard errors of the coefficients (S. E. Coef.) for three series of measurements and table 4 rists the constants of all related viscometers.

4. D i s c u s s i o n

For the viscometers not listed in the tables, the uncertainties of the variables temperature and time are approximately the same as for viscometer D I (table 2). The zero uncertainties given for some temperatures or times signify that the values obtained for one mesurement operation were predominantly identical. In the

case of several series of measurements, the method of least squares lead to results, which in most cases lead to greater deviations in the constants then in the case of single measurements. Therefore, the highest S. E. Coef. of one series of measurements are given along with the viscometer constants. When comparing the results obtained with eq. [1] it was found that the standard deviations (st. dev.) when evaluating eq. [il with n = 2 were approximately three times higher than when eq. [1] was evaluated with three parameters. Moreover, the K values obtained with the three-parameterequation [1] are always greater than those calculated with the two-parameter-equation [1] (table 5). Up to now, besides the above mentioned investigations (1), Cannon-Ubbelohde-viscometers have been calibrated by Korson et al. (5) at 20, 25, 30, 40, 50, and 60C with water data from the National Bureau of Standards, by Eicher et al. (2) at 20 and 40C with water data from Korosi et al. (7) and by Kingham et al. (6) at 5, 10, 15, 20, and 25 C with averaged water data from the literature. These authors found n to be 2, Eicher et al. (2) employed n = 2 in the v / t equation from the

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Table 5. Viscometer constants K, L (average from several series of measurements) and standard errors of the coefficients, in accordance with eq. [1] with n = 2, for KPG-Ubbelohde-viscometers Viscometer
K. 10 3

S.E. Coef. K
c m 2 " S -2

10 3

L
cm 2 s

S.E. Coef. L
cm 2 s

c m 2 " S -2

D D D D D A A

I II III IV V I II

3.0720 2.807 2.6515 2.887 3.0417 2.476 2.6503

0.0013 0.0014 0.0010 0.004 0.0018 0.003 0.0014

332.1 276.6 331.6 525.1 295.4 228.6 181.1

7.7 3.3 9.8 17.8 4.7 2.6 3.0

very outset. V e r y few k i n e m a t i c v i s c o s i t y / t i m e s value pairs were e m p l o y e d in the calculations o f m o s t p r o b a b l e values for these c a l i b r a t i o n o p e r a t i o n s . I n o n e case (6), the d y n a m i c viscosities f o r 5 a n d 1 0 C can n o t b e c o n s i d e r e d as reliable with the given d e c i m a l accuracy. D e t e r m i n a t i o n o f the H a g e n b a c h - C o u e t t e e r r o r shows h o w i m p o r t a n t exact d e t e r m i n a t i o n o f the v i s c o m e t e r c o n s t a n t s is. A l t h o u g h we used the s a m e t y p e o f K P G - U b b e l o h d e - v i s c o m e t e r s (0c), this e r r o r can differ e x t r e m e l y f r o m v i s c o m e t e r to viscometer. It can be seen f r o m the values f o r v i s c o m e t e r D I , listed in t a b l e 6, t h a t the d i f f e r e n c e b e t w e e n the H a g e n b a c h C o u e t t e errors o f viscometers D I a n d D IV a m o u n t to a b o u t 35% at 100 s a n d a b o u t 5170 at 400 s r e f e r r e d to v i s c o m e t e r D I. D u r i n g the c a l i b r a t i o n o f viscometers, if we p r e s u m e t h a t

n = 2, the v i s c o m e t e r c o n s t a n t K can be d e t e r m i n e d b y m e a s u r i n g the times at one t e m p e r a t u r e (e.g. r o o m t e m p e r a t u r e ) , h u t the results listed in t a b l e 7 show h o w i n c o r r e c t this m e t h o d can be. I f the H a g e n b a c h - C o u e t t e q u a n t i t y L * is given K can be d e t e r m i n e d b y m e a n s o f a m e t h o d o f iteration. W i t h o u t c o n s i d e r a t i o n o f the c o r r e c t i o n factors M a n d M u , this is r e l a t e d to the c o n s t a n t L in eq. [1] in the following manner:
L = L*/K 1/z ,

[4a]

L * itself can be c a l c u l a t e d with e q u a t i o n : L* = 1.66. V3/2/(l Dl/Z). [4b]

In eq. [4b], V signifies the v o l u m e o f the v i s c o m e t e r - t i m e b u l b , l is the length a n d D the

Table 6. Hagenbach-Couette error of KPG-Ubbelohde-viscometers in accordance with eq. [1] without correction factors M and M u, with mean (av.) viscometer constants K, L, n and the value from one single measurement as a function of the time. DI, DIV and DIIIa: Kinematic water viscosities of K o r s o n et al. (5) (eq. [3]), DIIIc: Kinematic water viscosities of the average of the literature (eq. [3]), DIIIb: Kinematic water viscosities of K o r s o n et al. (5) (eq. [5]), DIIId: Kinematic water viscosities of the average of the literature (eq. [5]). Viscometer DI av. D IV av. D IIIa D IIIb 3rd series of measurements
L/(K.
s

D IIIc

D IIId

time
s

t n)

100 125 150 175 200 225 250 275 300 400

8.99 6.65 5.20 4.22 3.53 3.01 2.61 2.29 2.04 1.38

14.95 11.72 9.61 8.12 7.02 6.18 5.51 4.96 4.51 3.30

8.20 6.30 5.08 4.24 3.62 3.15 2.78 2.49 2.24 1.60

8.28 6.40 5.20 4.36 3.74 3.26 2.89 2.59 2.34 1.69

8.21 6.40 5.21 4.39 3.78 3.31 2.94 2.64 2.40 1.74

8.28 6.40 5.20 4.36 3.74 3.26 2.89 2.59 2.34 1.69

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Table 7. Hagenbach-Couette correction factor n, Reynolds number Re and viscometer constant K of the KPGUbbelohde-viscometer D I as the function of the time (temperature) Series of measurement 1 2 1 1 2 1 2 1 2 1 2 Temperature C 17.085 17.032 21.042 24.990 25.076 33.015 33.028 53.020 53.107 68.999 69.023 Time s 351.89 352.29 319.40 291.93 291.37 247.08 246.91 175.38 175.24 141.47 141.52 k'Li 106 t m 2 s- 1 1.0793 1.0807 0.9788 0.8931 0.8913 0.7529 0.7527 0.5275 0.5268 0.4186 0.4185
n Re K.
10 3

cm2 s- 2 0.254 0.216 0.305 0.432 0.440 0.604 0.572 0.788 0.807 0.905 0.917 40.88 40.78 49.66 59.55 59.78 ~ 83.46 83.54 167.82 168.18 262.15 262.14 3.072 3.072 3.071 3.068 3.067 3.061 3.062 3.046 3.045 3.033 3.031

diameter of the capillary. The following values were specified by Schott for viscometer D I: V = 5.67ml, l= 9cm, D = 0.0465 cm.

As can be seen in table 7, K values were calculated which decreased as the Reynolds number increased. Although in the present case the K value for 17C agrees with the value calculated in eq. [1] (n = 2), the value of 208.35 for L is considerably smaller (see table 5). The KPG-Ubbelohde-viscometers were calibrated with water as very precise water viscosity data are available (2, 5, 7, 12). However, it was not possible to apply the viscosity data given by these authors as we calibrated the viscometers at other temperatures. Therefore, the viscosities were adjusted by a viscosity/temperature equation and it was found that by extensive calculations of most probable values that eq. [3] best describes the experimental viscosities (11). However, if we evaluated the same viscosity data with the equation given by E i c h e r et al. (2)
I1 = A . T ' . exp [ B / ( T - To)]

[5]

we would obtain viscometer constants which would not agree with the values calculated by

eq. [3] (tables 8 and 9). In eq. [5], the parameter n is a temperature coefficient of the viscosity; the other parameters in this equation have the same significances as those in eq. [3]. Similar results are obtained if measurements are based on other viscosity data. In the present case, the watet viscosity data from the literature (2, 7, 12, 13, 14, 15) were taken into consideration if they deviated no more than 0.270 from the water data (5) on which the calibration was based. This means that no more than three of the twelve viscosity data used hefe (5) (30, 35 and 40C) differed only slightly from the averages obtained from the literature data. In these cases also, the method of least squares shows that the viscometer constants K and n are modified only slightly but L is modified to a great extent (table 9). These viscometer constants can lead to Hagenbach-Couette errors which become greater as time increases (from about 1% at 100 s to 970 at 400 s). For example, in contrast, the viscosities calculated with the constant of viscometer D III only differed slightly from each other (about 0.8% at 100 s and about 1070 at 400 s). According to C a n n o n et al. (1), the functional relationship between the Hagenbach-

Table 8. Temperature coefficients of viscosity A, B, To, C and n (*values) calculated with various kinematic water viscosities in accordance with eq. [3] and [4] Eq.
3

Water data 15-70C

Korson et al. (5)

A 0.0101175 11945.6

B 93.750 187.074 93.996 185.337

To 206.781 190.606 206.899 191.101

C 1027.35 1.9734"

5 3 5

Average of the literature 0.010279 (see text) 12291.5

1023.10 - 1.9770"

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Rheologica Acta, Vol. 19, No. 5 (1980) 4~

77 77 77
eqOO ~D . t~ ~D 0 ~D 0

77
t'~ ,--~

Couette correction coefficient m (referred to below as correction coefficient m ) and the Reynolds number Re can be expressed as follows:

m = A 1 Re Az .
0
kOkID O 0 O 0 ~~D O 0 O 0 O 0

[6a]

~ c ~ cScS

O 0

In eq. [6a], A 1 and A 2 are coefficients which should result in the values A 1 = 0.037 and A 2 = 0.5 in all viscometers with trumpet-shaped capillary ends (1). By comparison, the correction coefficient m can first of all be derived from the expanded Hagen-Poiseuille law v = K.M. t m . V. (1 + Mu) 5/z [1"]

8.n.l.t
with this equation derived in this manner,

&
~D 4_a

8n.l.t V. (1 + Mu) 5/2 (K. M . t - v)

=

Az(.

2. V
~ . ( D / 2 i - v. t

)Az

[6bi

0oo

0 o '~t"

oOkO ',1 '-I

eelO~ ,-~ xl

06
O 0 O 0 O 0 O 0 O 0 O 0 0 o o O 0

oooo
O 0

c~ o c~ ~D

~5c5

cSd

e~eq 0

e,ioi e4e4
e~ tt~ o-~ tt~

O 0

O 0

0 0

~~
09 0 ~ eq

oo
+.a +.J ~_4 e

oo~
0 . ~ "~o

The values for the correction coefficient m (also the coefficients A 1 and A 2 not given here) were determined by means of calculations o f most probable values. In this case, the viscometer constant K was varied until eq. [6b] exhibited a minimum value of reduced Chi-square (10). For viscometers D V and A I I , the approximate viscometer dimensions V = 5.7 (2) ml; l = 9 cm and D = 0.046 (0.036) cm were used to evaluate eq. [6bi. As mentioned by other authors also (1 and 16), an increase in the correction coefficient m as the flow rate increased was ascertained with low Reynolds numbers (fig. 2 and table 7). The ra~Re dependence shown in figure 2 illustrates that functional relationship between m and Re cannot be described by a function with constant coefficients for the KPG-Ubbelohdeviscometers. Also in the case of the curve (not illustrated hefe) for m and Re o f the other KPGUbbelohde-viscometers, no m / R e function can be found with constant coefficients for different viscometers with the result that different time exponents n are obtained in evaluation of eq. [1] (see tables 3 and 4). Moreover, it is noteworthy that the ASTMviscometers calibrated by us (one of which is shown in fig. 2) exhibit a steeper increase in the m/Re curve than the DIN-viscometers. However, in the present measurements, only

Melsheimer and zaltay, Exaet calibration of KPG-Ubbelohde-v&cometers

I 35
.

667

E
(_ o ~J

(3

2
c o

1.20

o t_ c o o
i

1.05

txl

~-

b
0 U

.90

.75

u < m z <2 I

60

88

168 240 328 REYNOLDS- NUMBER RE

400

480

Fig. 2. Dependence of HagenbachCouette correction coefficient m on the Reynolds number Re for the KPG-Ubbelohde-viscometers AII (O), D I (V]) and DIV ( A ) - 3rd series of measurements

one r a n g e o f R e y n o l d s n u m b e r s u p to a b o u t 400 were r e g i s t r a t e d a n d n o t u p to m o r e t h a n 2000 as in the case o f Cannon et al. (1) w h o s e t h e o r e t i c a l a n d e x p e r i m e n t a l investigations led to a value n = 2. T h e r e f o r e , capillaries with t r u m p e t - s h a p e d ends, for which n s h o u l d have the value 2 (1, 3), were c o n s e q u e n t l y n o t used. This also h o l d s true for capillaries with s q u a r e ends, for w h i c h n = 2 / 3 (3) is given.

References
1) Cannon, M. R., R. E. Manning, J. D. Bell, Anal. Chem. 32, 355 (1960). 2) Eicher,, L. D., B. J. Zwolinski, J. Phys. Chem. 75, 2016 (1971). 3) Van Wazer, J. R., R. E. Colwell, K. Y. Kim, J. W. Lyons, Viscosity and Flow Measurements - A Laboratory Handbook of Rheology, Interscience, Wiley (New York 1963) 4) Caw, W. A., R. G. Wylie, Br. J. Appl. Phys. 12, 94 (1961). 5) Korson, L., W. Drost-Hansen, J. Millero, J. Phys. Chem. 73, 34 (1969). 6) Kingham, J., W. A. Adams, J. MeGuire, J. Chem. Eng. Data 19, 1 (1974). 7) Korosi, A., B. M. Fabuss, Anal. Chem. 40, 157 (1968). 8) Hardy, R. C., Nat. Bur. Stand. Monograph 55 (1962). 9) Bowman, H. A., R. M. Sehoonover, J. Res. Nat. Bur. Stand. 71C, 179 (1967). 10) Bevington, P. R., Data Reduction and Error Analysis for the Physical Sciences, McGraw-Hill (New York 1969). 11) Melsheimer, J., K. Langner, Ber. Bunsenges. Phys. Chem. 83, 539 (1979). 12) Hardy, R. C., R. L. Cottington, J. Res. Nat. Bur. Stand. 42, 573 (1949). 13) Geddes, J. A., J. Am. Chem. Soc. 55, 4832 (1933). 14) Coe, J. R., Jr., T. B. Godfrey, J. Appl. Phys. 15, 625 (1944). 15) Weber, W., Z. Angew. Phys. 7, 96 (1959); 15, 342 (1963). 16) Weber, W., W. Fritz, Rheol. Acta 3, 3 (1963). Authors' address: Dr. J. Melshei_mer, N. E. zaltay Fritz-Haber-Institut der Max-Planck-Gesellschafl Faradayweg 4 - 6 D-1000 Berlin 33

Summary
KPG-Ubbelohde-viscometers f o r low viscosity 'fluids were exactly calibrated with an automatic viscosity measuring system from Schott by performing measurements on tridistilled watet as a function of the temperature. The time exponent in the Hagenbach-Couette correction term is not, as theoretically determined by Cannon et al., equal to 2 but lies between 1.09 and 1.79 in the case of the identical KPG-Ubbelohde-viscometer types put to use in our experiments. Calibration of such viscometers with one fluid at one certain temperature can lead to high viscosity errors in the case of brief flow times.

Zusammenfassun9
KPG-Ubbelohde-Viskosimeter fr niedrigviskose Flssigkeiten wurden mit einem automatischen Viskosittsmesystem der Fa. Schott durch Messungen von tridestilliertem Wasser in Abhngigkeit von der Temperatur exakt kalibriert. Der Zeit-Exponent im Hagenbach-Couette-Korrekturglied ist nicht wie von Cannon et al. theoretisch abgeleitet gleich zwei, sondern liegt fr die eingesetzten KPG-UbbelohdeViskosimeter gleichen Typs zwischen 1,09 und 1,79. Die Kalibrierung solcher Viskosimeter mit einer Flssigkeit bei einer bestimmten Temperatur kann fr kurze Ausfluzeiten zu greren Viskositts-Fehlern fhren.