Joshua Cunningham

Surface Tension of n-Butanol Solutions CHEM 417 Due: 3/20/2008 Partner: Laura Homsey

Introduction
After being amazed by the apparent magic of waters high surface tension as children, most of us think little of the consequences of this interesting property of liquids. Surface tension plays a part in many common effects seen every day: a water stream breaking into droplets and the beading of water on a smooth, non-polar surface are just two examples. In this lab, we became closely acquainted with the surface tension of an aqueous solution and what effects it had on surface concentration. We combined pure n-butanol with water in various concentrations to see how much effect it would have on the surface tension. Plotting the value of gamma (surface tension) in units of g/s2 for each of the concentrations presented a linear relationship. The slop of the line gave us what we needed to find the surface concentration using the Gibbs isotherm equation. Finally, we used this value to find an experimental molecular crosssectional area which we compared to a theoretical one using computer-built molecular models. Real-world applications of surface concentration and surface tension might be found in industries requiring precise control on fluid dynamics or homogenous distribution of solutes in solution. Molecular cross-sectional area has implications in molecular collisions and the energy found therein.

Experiment and Data

For this experiment, we were charged with measuring the surface tension of aqueous solutions of n-butanol. This experiment spanned over the space of two lab periods; during the first period we became acquainted with the instrument and made the solutions and during the second we took measurements. On the first day, we started by cleaning the sensor wire. We carefully removed the wire from its hanger and used a kim wipe soaked in methanol. After this, we wiped the glass surface tension tray with methanol and let it air dry. The instrument used was a DeltaPi Single-Channel Microtensioner made by Kibron Inc. In order to calibrate the sensor, we filled one of the compartments with deionized water and submerged the sensor wire by turning the knob to lower the sensor arm. Once the tip was submerged, we slowly raised the wire out until it was visibly pulling the surface of the water up.

Figure 1 - Inserting the sensor wire into liquid

We opened the Delta Graph program and clicked on the "Measure" button. We were calibrating with water so the tension difference was set at 72.8 mN/m.

We clicked on "Calibrate" and the software guided us through the process (sensor in air, take reading, sensor in water, take reading). The readings were as follows:

Label Air Water Coefficient

Value -148 mV 626 mV 65.6 mV/mg

Table 1 - data gathered from calibration

Next, we needed to zero the machine out so our readings would have a baseline reading removed. We took a reading in air and then took a reading in water. The gamma value for water stayed at 69.0 mN/m 0.1 for several minutes before we stopped the reading. This value was not needed for any readings but we were prepared to repeat it when the actual data was collected. Note: uncertainty for the surface tension reading is discussed later in this report. We needed 8 different aqueous solutions of n-butanol of various different concentrations, the first being 100 mL at 0.8M. Butanol has a molar mass of 74.12 g/mol and a density of 0.8 g/ml. The molarity was calculated as follows:

The actual weight of the butanol obtained was 6.001 0.001 g so the molarity was:

To achieve this molarity, we added the 6.001 g of butanol to a glass volumetric flask and filled it up to the line (100 mL) with deionized water. After shaking the mixture for about one minute, we measured out 75 mL using a graduated cylinder and transferred this to a new 100 mL volumetric flask. This was also filled to the line with deionized water and shaken thoroughly. The new molarity was calculated as follows:

This was repeated six more times for a total of 8 solutions. All molarities are listed below:

Starting molarity (M) n/a 0.810 0.607 0.455 0.342 0.256 0.192 0.144

x x x x x x x x

Dilution factor n/a 0.75 0.75 0.75 0.75 0.75 0.75 0.75

= = = = = = = =

Final molarity (M) 0.810 0.607 0.455 0.342 0.256 0.192 0.144 0.108

Table 2 - Molarities of n-butanol solutions

We stoppered the flasks containing our mixed solutions and set them aside for the next lab period. When we reconvened, we made sure to clean the liquid trough and the wire carefully with methanol and set about calibrating and zeroing our instrument as before. Calibration values were within 2 mV of our first reading and the gamma value was the same as before, 69.0 mN/m +/- 0.1.

Once the trough had dried completely, we filled 8 different depressions with the 8 solutions, making careful note of which depression held which molarity. We started collecting data with the lowest molarity solution first (0.108 M). The sensor wire was lowered into the solution, then raised until the solution stretched to meet the wire (see figure 1). In the Delta Graph, we clicked Start to begin the reading. We left the instrument reading until the gamma reading settled into a range.

Results and Calculations

The surface tension () values are recorded below along with their corresponding molarities. Estimated uncertainty for all readings is 0.2 mN/m and was found by watching the range of fluctuation for the gamma measurements.

c = Molarity (M) 0.810 0.607 0.455 0.342 0.256 0.192 0.144 0.108

ln(c) -0.211 -0.499 -0.787 -1.07 -1.36 -1.65 -1.94 -2.23

(mN/m) 57.4 0.2 54.6 0.2 51.4 0.2 46.8 0.2 42.3 0.2 39.8 0.2 35.2 0.2 30.3 0.2

Table 3 - Gamma values for each molarity

This data was plotted in Excel as surface tension in mN/m as a function of the natural log of concentration.

Surface Tension as a Function of Concentration

70 Surface Tension (mN/m) 60 50 40 y = -13.461x + 28.324 13.461x R = 0.9946 30 20 10 0 -2.5 -2 -1.5 -1 -0.5 0 0.5 Natural log of Concentration

Using the Excel LINEST function, we determined the slope, Y intercept, and the uncertainty of each. Y-intercept,

The percent uncertainty for the slope can be found as follows:

Using the uncertainty percent, a range of acceptable values can be found by plugging the X value (natural log of concentration) into the line equation given by Excel and solving for Y (surface tension).

X value (ln[c]) -0.211 -0.499 -0.787 -1.07 -1.36 -1.65 -1.94 -2.23

Slope uncertainty 2.93% 2.93% 2.93% 2.93% 2.93% 2.93% 2.93% 2.93%

Y () 58.3 54.4 50.5 46.7 42.8 38.9 35.0 31.1

High Y value 60.0 56.0 52.0 48.1 44.1 40.1 36.0 32.0

Low Y value 56.6 52.8 49.1 45.4 41.6 37.8 34.0 30.2

Actual 57.4 0.2 54.6 0.2 51.4 0.2 46.8 0.2 42.3 0.2 39.8 0.2 35.2 0.2 30.3 0.2

Acceptable?

Table 4 - Uncertainty of slope versus recorded data

From the slope, the surface concentration, , can be found. According to chapter 10 in the Shoemaker text (page 343), is found via the following equation, the Gibbs isotherm:

The second term, change in gamma over the change in the natural log of concentration, is the slope of the line, m. Plugging the slope into the Gibbs isotherm equation, we find:

We are looking for surface concentration in units of mole/m2 so we need to convert:

The uncertainty for this calculation was found using the percent uncertainty for the slope found above (2.93%). To find the effective experimental cross-sectional area of butanol, we need to take the gamma value from above and determine the number of molecules that can be found in that area using Avogadros number:

So

To estimate the actual effective cross sectional area of butanol, a model was constructed:

Figure 2 - Space-filling model of n-butanol

The model above was constructed with the appropriate bond distances and van der Waals radii. The plane of the molecule containing all carbon atoms and the oxygen atom is parallel with this sheet of paper. It is clear that the molecular cross-sectional area is basically controlled by the bond lengths and radii of the carbon and oxygen atoms. The relevant measurements are as follows:

Distance Bond between sp3 carbons* Bond between sp3 carbon and oxygen* Bond between hydrogen and carbon/oxygen* Van der Waals radius of carbon Van der Waals radius of oxygen Van der Waals radius of hydrogen
Table 5 - Relevant molecular distances

Value () 1.51 1.42 1.11 1.89 1.52 1.20

(* indicates a value obtained from Careys Organic Chemistry, 5th Edition)

In order to calculate the area, the model must be sliced in half through the plane of the molecule and the bond lengths and van der Waals radii examined carefully. This was accomplished by converting the space-filling into a stick model and finding measurements by pixels in a graphics program. This is illustrated below:

Figure 3 - Calculation of cross-sectional area based on measurements in pixels

Discussion and Conclusions

The theoretical value for the cross-sectional area, 38.5 2 is about 25% larger than the high end of the 30.2 0.9 2 sectional found through our experiment. There are clearly factors at work here that can explain the discrepancy. nt. First, it is clear by looking at a shadow of the molecule that calculating an area for a rectangle that contains the molecule is no more than a rough estimate. The white space in the graphic to the left indicates area that is included in the theoretical calculation but is not part of the molecules actual cross sectional area. Though it is difficult to guess the exact cross-sectional amount that this method overestimates, it must be at least over 2 if not quite 20% a bit more. Already, we have accounted for a good portion of the difference. Additionally, the rest might be explained by looking at how the two numbers were derived. The butanol model in Figure 2 was constructed outside of the influence of other molecules. This is the estimated radius of a completely free molecule of butanol floating through space a condition not replicated in our experiment. To obtain the experimental effective area, we measured surface tension in a liquid giving us a surface concentration of butanol. Butanol molecules rface will exhibit hydrogen bonding with each other which will increase the amount of molecules per unit area and lower our calculated area. In the same vein, the molecules that affected our surface tension and contributed to the surface concentration will not all be in the same plane, as our calculation assumes. Some molecules may have their plain roughly parallel to the surface of the solution while others might be perpendicular or anywhere in between. Just like our theoretical calculation of area based on rough measurement includes obvious oversight, an estimation of area using experimental data has clear shortcomings. Despite the large margin for over and under-estimation, the two overunder figures came within a fairly close margin.