Transport Properties and Chemical Kinetics

Noah Shandor, A.J. Lewis, Nick Bigham, Caleb Ancharski 2/21/18

Abstract:
Solutions containing 40% and 60% methanol by mass with water are analyzed with an Ostwald
viscometer. The viscosities were found to be 1.541 𝑚𝑃𝑎 ∙ 𝑠 and 1.482 𝑚𝑃𝑎 ∙ 𝑠 respectively.
These solutions are determined to not be ideal after a comparison of fluidities with ideal mixtures
with a percent error of 49.40% and 52.10% respectively. The plot of the inverse temperature vs.
the natural log of the viscosities of water at different temperatures gave the Arrhenius parameters
𝐴 and 𝐸𝐴 with values of 1.50 × 10−3 𝑚𝑃𝑎 ∙ 𝑠 and 1.549 × 101 𝑘𝐽 respectively. The percent
errors for these values were 9.62% and 1.73% respectively. This small percent error proves that
our results for this experiment are valid.
Introduction:
Viscosity is most commonly defined as the resistance to flow. However, a more useful definition
is that viscosity is a resistive force that is proportional to the gradient of flow velocity of a fluid.1
This basically means that viscosity occurs due to friction between adjacent “layers” of fluids.
This definition will be the basis for our derivations. The viscosities of pure water and pure
methanol have been investigated2,3 and the purpose of this experiment is to see how these values
relate to a mixture of both compounds. Viscosity has also been shown to be temperature
dependent; as temperature increases, viscosity decreases. Mixtures have been shown to either be
ideal or non-ideal. Ideal mixtures will behave as if the interactions between the constituents are
the same as the interactions with the pure mixtures where non-ideal mixtures have separate
interactions when mixed1. This experiment will determine if a methanol/water mixture is ideal or
non-ideal.
Theoretical Basis:
First, we assume a liquid is flowing smoothly in the 𝑥 direction and that the liquid is made of an
infinite number of sheets with a cross section 𝑑𝛼. If one sheets velocity 𝑣𝑥 exceeds the adjacent
sheets velocity by an amount 𝑑𝑣𝑥 , and the adjacent sheet is displaced by a distance 𝑑𝑧, then the
force to continue the motion or flow is given by:4
𝑑𝑓𝑥 𝜕𝑣𝑥
= 𝜂( ) (1)
𝑑𝛼 𝜕𝑧 𝑧
𝜕𝑣
Where 𝜂 is the viscosity coefficient and ( 𝜕𝑧𝑥 ) is the tangential velocity gradient that depends on
𝑧
the distance to the wall of the tube 𝑧. A variation of this equation was derived by Poiseuille in
18444:
𝑑𝑉 𝜋𝑟 4 𝛥𝑃
= (2)
𝑑𝑡 8𝜂𝐿
 𝑑𝑉
Where is the volume flow rate of the liquid, 𝑟 is the radius of the tube, and 𝐿 is the length of
𝑑𝑡
the tube. Δ𝑃 is the pressure behind the force that is creating flow. For this equation we assume
that this value is constant and slow. Using this assumption, the equation can be integrated and
solved for the viscosity coefficient:
𝜋𝑟 4 𝑃𝑡
𝜂= (3)
8𝑉𝐿

Where 𝑡 is the elapsed time and 𝑉 is the volume of the liquid passing through the Ostwald
viscometer. We assume that the volume of liquid is constant and the pressure is proportional to
the density of the liquid 𝜌. We can group the constants that are left into one general constant 𝑘.
This leaves the simple equation of:

𝜂 = 𝑘𝜌𝑡 (4)
This equation is used to determine 𝑘 for the Ostwald viscometer by timing water at 25℃, 35℃,
and 45℃ as it flows across two fiducial marks. This average k is used with equation (4) to
determine a viscosity coefficient of the methanol water mixtures.
Another useful property of liquids is fluidity, designated at F below. This is simply defined as the
inverse of the viscosity coefficient4,
1
𝐹= . (5)
𝜂

This is useful to us because fluidities of mixed solutions are additive. Knowing this, an equation
useful for determining ideality can be derived, where 𝑥𝐴 is the mole fraction of methanol and 𝑥𝐵
is the mole fraction of water4:

𝐹 = 𝑥𝐴 𝐹𝐴 + 𝑥𝐵 𝐹𝐵 (6)
Using the mole fractions of methanol and water in each solution an ideal fluidity is determined
and compared to the experimental fluidity.
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑀𝑒𝑡ℎ𝑎𝑛𝑜𝑙
𝑥𝐴 = (7)
𝑇𝑜𝑡𝑎𝑙 𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑊𝑎𝑡𝑒𝑟
𝑥𝐵 = (8)
𝑇𝑜𝑡𝑎𝑙 𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛

The final useful relationship is based on the temperature dependence of viscosity. This equation
was first derived by Arrhenius in 19124:
𝐸
𝜂 = 𝐴 exp ( 𝐴 ) (9)
𝑅𝑇
1
This equation is proved graphically by fitting a linear curve to a plot of ln(𝜂) against 𝑇. The
𝐸𝜂
slope for this graph is equal to .
𝑅
Results:
Determination of 𝒌.
An Ostwald viscometer is used and the time for water to pass from the top fiducial mark to the
bottom fiducial mark is recorded for three trials and three temperatures and averaged. These
times are found in Table 1. Literature values for the viscosity coefficient of water at these
temperatures were explored5 and using equation (4) three values of 𝑘 were calculated and
averaged. These values are also found in Table 1.

Table 1. Recorded times for water at 25, 35, and 45℃ and the values for 𝑘 with calculated
averages
Substance Time 1 Time 2 Time 3 Average Time Value of 𝑘 Average 𝑘
(seconds) (seconds) (seconds) (seconds) 𝑚𝑃𝑎∙𝑚𝐿 𝑚𝑃𝑎∙𝑚𝐿
( 𝑔 ) ( 𝑔 )
Water 25℃ 59.09 60.32 60.06 59.82 1.492 × 10−2
Water 35℃ 52.19 48.37 47.97 49.51 1.461 × 10−2 1.471 × 10−2
Water 45℃ 41.53 41.19 40.94 41.22 1.460 × 10−2

Determination of 𝜼
The methanol solutions were tested in the same manner as water. These times are found in Table
2. Using equation (4) with the average 𝑘 calculated previously, an experimental value for the
viscosity coefficient is reached. Equation (5) was used to determine fluidity. Both of these values
are found in Table 3.
Table 2. Recorded times for 40% and 60% methanol with the calculated average
Mixture (25℃) Time 1 Time 2 Time 3 Average Time
(seconds) (seconds) (seconds) (seconds)
40% Methanol 110.44 111.47 111.03 110.98
60% Methanol 107.06 108.16 117.19 110.80

Test of Ideality
After the viscosities were determined, the solutions were compared to ideal versions of the same
solutions. These comparisons are made with the use of equation (5). The mole fractions of each
compound in the mixture was determined and multiplied by its respective fluidity. These two
values were added and the resulting fluidity is considered the ideal fluidity for that mixture.
Accepted fluidity values for methanol and pure water were researched.2,3 These values are also
found in Table 3. A percent error was calculated treating the experimental value as the actual and
the literature value as the experimental. This gives values of 49.40% and 52.10% for 40% and
60% solutions respectively.
Table 3. Values for the viscosity and the experimental and ideal fluidity of the two
methanol/water mixtures
Mixture Viscosity (𝑚𝑃𝑎 ∙ 𝑠) Experimental Fluidity Ideal Fluidity
1 1
((𝑚𝑃𝑎∙𝑠)) ((𝑚𝑃𝑎∙𝑠))
40% Methanol 1.541 0.649 1.283
60% Methanol 1.482 0.675 1.409

1
The final calculation was to determine the Arrhenius parameters. This is done by plotting 𝑇 vs.
ln(𝜂) in MATHCAD and is found in Figure 1. The experimental parameters were compared to
known parameters and a percent error is found. The value for 𝐴 is 1.50 × 10−2 𝑚𝑃𝑎 ∙ 𝑠 and for
𝐸𝐴 is 1.55 × 10−2 𝑘𝐽.

1 𝐸𝐴
Figure 1. A plot of 𝑇 against ln(𝜂). The slope of this curve is equal to and the intercept is
𝑅
equal to the ln(𝐴)
Discussion:
The accepted value for the Arrhenius parameters are 1.66 × 10−3 for 𝐴 and 1.52 × 101 for 𝐸𝐴 .
This gives a percent error from the experimental values of 9.62% and 1.73% respectively. This is
a relatively small error so it is safe to say the experimental results are close to the accepted
results and therefore any conclusions drawn from this data can be valid. As for the viscosity
measurements the experiment went well. The results show that as temperature increases the
viscosity coefficient decreases. It is also shown that the mixtures of methanol and water have a
higher coefficient of viscosity than just water by itself. This means that some other
intermolecular force or factor is causing the liquid to resist flow more than if it were in its pure
state. This information also supports the data found in Table 3. Due to the large difference in
experimental fluidity and ideal fluidity the mixed solutions of methanol and water can be
assumed to not be ideal. The intermolecular forces at work most likely causing this non-ideality
is the repulsion of the non-polar and polar parts of the molecules. The hydroxyl groups on either
molecule are attracted to each other due to partial charges as a result of electronegativity
differences. Because of the attraction between methanol and water, the polar part of molecules
will act as they do in a pure solution but due to the non-polar 𝐶𝐻3 the molecules do not slide past
each other as fluidly and are non-ideal. This is proven by the percent errors of the 40% and 60%
solutions being 49.40% and 52.10% respectively. The temperature dependence of viscosity is
also shown in the results of this experiment. Table 1 shows that as the temperature was
increased, the flow rate increased. This can directly be related to viscosity and proves that as
temperature increases, the viscosity decreases. This can most likely be attributed to the increase
in particle speed as temperature is the average kinetic energy of the particles in a sample.

Conclusion:
This laboratory experiment accurately demonstrates the effect of mixed solutions on viscosity. If
the two solutions that are mixed interact with each other intermolecularly the viscosity will
increase due to these interactions. The polar part of the methanol/water mixture feels the effects
of the non-polar part of the methanol and the solution flows less quickly. Because of this
phenomenon the methanol/water mixture is non-ideal. The small percent errors from the
Arrhenius calculations proves our results are accurate and dependable.
References:
(1) Shoemaker, D. et al. Experiments in Physical Chemistry, 8th ed.; McGraw-Hill: New
York, 2009.
(2) Van der Leeden et al. The Water Encyclopedia, 2nd ed.; Lewis Publishers: Chelsea, 1990.
(3) Haynes, W.M. CRC Handbook of Chemistry and Physics, 91st ed.; CRC Press Inc.: Boca
Raton, 2010
(4) Helpern, Arthur M. and McBane, George C., Experimental Physical Chemistry: A
Laboratory Textbook; W.H. Freeman and Company: New York, 2006.
(5) Lawrence, K.; Walter, D.; Frank, M. Viscosity of water at various temperatures. The
Journal of Physical Chemistry 1969, 73, 34-39.