PHY 263 Practical Experiment : Viscosity Measurements with the Falling Ball Viscometer

ALISSA KRIEL 11123002 Practical performed on 30 August 2013 (Group 2 , Friday session)
Immediate Laboratory partner : S. Congolo Other group members : M.L. Jacobs, K. Van Der Laarse

Abstract
In this practical investigation the objective was to quantify the physical liquid property of viscosity for a motor oil to observe what influence heightened temperature would have on its physical composition and behaviour. The use of a falling sphere viscometer proved successful to achieve this. The time for a spherical metal ball of known density to fall through a measured distance in the thermally equilibrated oil was measured and via a theoretical relation the dynamic and kinematic viscosity was computed. The motor oil viscosity measurements at successively higher temperatures agrees with trend of viscosities for most other liquids in that an increase in temperature resulted in a decrease in viscosity and density due to expansion of the molecular motion. This is a tendency worth noting regarding motor oils vast range of applications in, for example, combustion engines which become quite hot. Therefore care ought to be taken when designing carrier vessels and the like for such a substance.

The measurement of a motor oils Dynamic and Kinematic Viscosity at elevated Temperatures with estimation of the Molar Activation Energy required to overcome Internal Friction

Introduction
All fluids gases and liquids alike, have a physical property called Viscosity. In day to day standard ambient conditions the viscosity of gases are not intuitively noticed, although those of liquids are. Generally the viscosity of a liquid is thought of as its thickness but this notion is unsophisticated as the actual intrinsic cause of a liquids resistance to flow is the interactions of the intermolecular forces as layers of the fluid attempt to pass over one another. (Whittaker A.G. et al., 2005, p.15-17) The characterization of a liquids viscosity is quite necessary when design of containers, storage conditions of the liquid and most significantly applications where the liquid will be employed- in instruments for example. In order to effectively design and handle liquids, a good overall understanding of its chemical and physical properties is important viscosity being one such property. A commonly used and vital liquid encountered indirectly quite often is motor oil. It has extensive applications in almost every manufacturing industry among many others. Its behaviour under elevated temperatures can be of great interest and concern in applications where such temperature increases occur. To quantify this property of resistance to flow or resistance to a shearing stress, there are two related measures of viscosity, known as Dynamic Viscosity and Kinematic Viscosity. Dynamic Viscosity , , is a measure of the internal resistance between planes of liquid that is described by the Force necessary to move parallel molecular layers a distance dx apart over one another when a relative velocity v exists between them : (Rethwisch D. G. & Callister W. D ,2010, 488)

Stokess law further manipulates the definition by considering only a spherical molecule with radius r within the liquid that is influenced by the force F and 1/ : v=

................

Equation 1

One can consider the downward motion of a sphere under influence of Newtons gravitational law on Earth by means of the gravitational acceleration constant g as:

......... Equation 2 6

By using a commercial falling sphere viscometer, one can eliminate the 2r2/v term by use of a calibrated spherical constant obtained by letting a sphere of known composition drop through a liquid of known density. This constant can be called K. (PHYWE, 2008, p 58)

22 ( ) = ...........Equation 3

..........Equation 4 In the above two equations, the density difference term is the difference between the density of the sphere causing a shearing stress as it passes through the liquid and that of the liquid itself. t arises as the time it would take for the sphere to fall some distance. Most liquids experience a decrease in viscosity as their temperature is increased. This relates to the provision of extra energy that can be used to help overcome the internal energy barrier that exists as a resistance to the aforementioned planes of liquid as they move over each other. This internal energy is related to the viscosity by:

1/

........Equation 5

The parameter C is dependent on the experimental conditions, whilst R is the universal Gas constant. The other viscosity quantification is the Kinematic viscosity which is simply the ratio of the dynamic viscosity to the liquids density, / .

Method:
The equations 4 and 5 were employed to determine a motor oils dynamic viscosity, kinematic viscosity as well as the internal energy barrier E of the molecular resistance to motion. A falling sphere viscometer was utilised so that Equation 4 could be simply used. An Fe-Ni ball of diameter 15.578 mm and density 8.125 g/cm3 was selected as the sphere. The motor oils viscosity was determined at several temperatures ranging from 30oC to 70oC by measuring the time it took on average at a temperature for the ball to fall the calibrated 100.00 mm distance through the viscometer. Temperatures were monitored using thermometers. To finally be able to calculate the dynamic viscosity, it was necessary to also determine the motor oils density at the various temperatures. To do this, a pycnometer was used to weigh a certain quantity of oil at the same temperatures the rate of fall was measured at, which was related to its density.

Calculating the kinematic viscosity and the internal energy barrier could then be done by theoretical relations and calculations.

Results:
Below are tables containing both directly measured and processed data required to calculate the sought parameters and viscosities. In particular, mass and calculated density values for the motor oil are given first, where after the particulars of the Ni-Fe alloy ball used in the Viscometer is given. The accordingly calculated dynamic Viscosity and kinematic viscosity of the oil follows, as well as linearised data used to generate a plot to find the activation energy E viz. Equation 5.

Table 1: Pyncometer particulars* Mass of dry and clean Pycnometer (g) 20.640 *As from provided data of calibration. Table 2: Measured Pycnometer + oil masses at increasing Temperatures & calculated oil densities at these Temperatures Volume of Pycnometer (cm3) 24.628

Temperature (oC)

Mass of Pycnometer & oil (g) 0.01 g

Mass of oil* at T (g) 0.01 g

oil **, density of

oil at T (g/cm ) 0.0004 g/cm3
3

oil , density of
oil at T (kg/m3) 0.004 x 102 kg/m3
8.673 x 102 8.628 x 102 8.588 x 102 8.572 x 102 8.523 x 102 8.490 x 102 8.446 x 102 8.397 x 102 8.373 x 102

30 = 303 K 35 = 308 K 40 = 313 K 45 = 318 K 50 = 323 K 55 = 328 K 60 = 333 K 65 = 338 K 70 = 343 K

42.00 41.89 41.79 41.75 41.63 41.55 41.44 41.32 41.26

21.36 21.25 21.15 21.11 20.99 20.91 20.80 20.68 20.62

0.8673 0.8628 0.8588 0.8572 0.8523 0.8490 0.8446 0.8397 0.8373

*Mass of oil is calculated as the difference in total mass of pycnometer mass of dry and clean pycnometer , i.e. for 30oC : 42.00 g 20.640 g = 21.36 g

** oil is calculated using equation and the mass and volume data indicated in Table 1 & 2 as follows: i.e. for 30oC, = ( ) ()
21.36 24.628 3

= 0.8673 g/cm3

The ball used in the time measurement section had the following physical properties: Table 3: Physical properties of Ni-Fe spherical ball used in Viscometer Spherical constant K* ( mPa.s.m3/(kg.s) ) 16.0820 15.578 8.125 x 103 0.00012312

Mass (g)

Diameter (mm)

ball (kg/m3)

*The spherical constant K initially appeared as a value of 0.12312 mPa.s.cm3/(g.s) in the equipment certificate. It was converted to SI units via conversion factors.

Table 4: Time measurements for Ni-Fe ball to fall a unit distance 100.00 mm through the motor oil at various temperatures Mean Falling Time (s) 0.5 s 303 308 313 178.2 154.7 123.8 Dynamic Viscosity * (mPa.s) 0.4 mPa.s 159.2 138.3 110.8 1.84 x 10-4 1.60 x 10-4 1.29 x 10-4 Kinematic Viscosity (m2/s)

Temperature (K)

318 323 328 333 338 343

87.3 67.0 57.2 49.8 41.2 30.2

78.1 60.0 51.2 44.6 37.0 27.1

9.11 x 10-4 7.04 x 10-5 6.03 x 10-5 5.28 x 10-5 4.41 x 10-5 3.24 x 10-5

*The dynamic Viscosity, , was calculated using Equation 4 with all units in SI format.

e.g. for 303 K : = (0.00012312 mPa.s.m3/(kg.s)) x (178.2 s) x (8.125 x 103 - 8.673 x 102 ) kg/m3 = (159.2 0.4) x 10-3 = 159.2 0.4 mPa.s
.

Table 5 : Linearised dynamic viscosity values and corresponding Temperature reciprocals for motor oil data from Table 4 ln() 0.003 -1.84 -1.98 -2.20 -2.55 -2.813 -2.972 -3.11 -3.30 -3.61

(K-1)

3.30 x 10-3 3.25 x 10-3 3.20 x 10-3 3.15 x 10-3 3.10 x 10-3 3.05 x 10-3 3.00 x 10-3 2.96 x 10-3 2.92 x 10-3

0 2.9 -0.5 -1 -1.5

Graph 1: Linearised plot of Dynamic Viscosity versus reciprocal Temperature for motor oil
3 3.1 3.2 3.3 3.4

y = 4592x - 16.95 R = 0.988

ln()

-2

Graph 1: Linearised plot of Dynamic Viscosity versus reciprocal Temperature for motor oil Linear (Graph 1: Linearised plot of Dynamic Viscosity versus reciprocal Temperature for motor oil)

-2.5 -3 -3.5 -4

1/T X 10-3 (K-1 )

Via equation 5 , the linearised plot of Graph 1 is the plotted linear function resulting when : 1 ln = ln( ) + ( )

It will have a slope equal to J.K-1.mol-1.

, where R is the universal Gas constant with a value of 8.314

ln( ) = ln( ) +

1 ( )

The molar activation energy E, needed to overcome the internal friction which is intrinsically the cause of viscosity, can thus be calculated : Eoil = slope x R =
(ln()) ( )
1

xR

= 4592 K x 8.314 J.K-1.mol-1 = 38.2 kJ/mol

Discussion
The results obtained for the dynamic viscosity of the oil matches the theoretically expected trend which is a decrease in viscosity as temperature of the liquid is raised. This expectation is due to the external thermal energy supplying energy as such to the liquid which can be used to overcome the intermolecular resistance to motion. The dynamic viscosity is sometimes referred to as the absolute viscosity. This is because its mathematical definition relates to the actual force required to let two sections of the liquid move over one another by overcoming the intermolecular force friction. It also incorporates the shearing stress which is what ultimately acts as the force. Kinematic viscosity is a derived relation from the dynamic definition, and it is useful as it incorporates the density of the liquid. The decreasing density also indicates the microscopic increase in molecular energies as such. There are many sources of possible determinate errors for example the human error involved in lapping a time interval with the stopwatch to clock the time it took for the sphere to fall through the unit length in the oil. In order to try and minimize this error as much as possible, two observers clocked times and an average time was recorded. Another possible source of a determinate error is encountered at the calculation of density whereby a supposedly externally dry pycnometer filled with oil is to be weighed. It is important to weigh the meter before significant amounts of thermal heat have been lost to the surroundings in order to get an accurate mass value for the volume of oil at a particular temperature. This could lead to incomplete drying and subsequent weighing errors that could cause a bias in results. The linearised plot is not exactly linear, as might be expected from a theoretical point of view. The activation energy computed from the slope of the plot makes physical sense however, and it is useful to recall that the two major factors that determine a liquids viscosity is the actual internal structure of the molecules and the planes of molecules in the liquids intermolecular interactions when theyre moving with respect to one another and the temperature of the liquid. The activation energy of water is 14.8 kJ/mol (PHYWE, 2008, p. 60), and H2Os viscosity is generally much lower than the motor oils. It can be expected that the motor oil would have a much larger activation energy in this case.

Conclusion
The results of the kinematic and dynamic viscosity of the motor oil indicated that its viscosity decreased markedly with increases in temperature that were not vast. The behaviour of the liquid indeed matches the theoretical prediction that the viscosities of different liquids are different and sensitive as a function of temperature. Not all liquids behave similarly in the magnitude by which the viscosity is affected, and thus care needs to be taken when design opportunities regarding such substances are considered. This shows firstly that the motor oil behaves as most other liquids do expanding upon being heated and decrease in its viscosity. Secondly, the results indicate that both the Dynamic and Kinematic viscosity decrease. This is something to bear in mind when the oil could be subjected to thermally unstable or high temperature applications. The experimental results were quite useful in quantifying the viscosity property of the liquid and how it is influenced by ambient temperature.

References:
-A.G. Whittaker et al., 2005, Instant notes in Physical Chemistry, p. 10-25 -Rethwisch D. G. & Callister W. D., 2010, Materials Science and Engineering, An Introduction, p. 488, 531 -PHYWE Physics laboratory experiments manual, 2008, p 56 60