Lab #6: Chemical Engineering

February 3, 2012 Ian Ip 10011223 Section 5 Email: 0imhi@queensu

Lab partner: Blair Hanbury APSC100 Module 2

ABSTRACT
The aim of the experiment is to create and investigate the properties (both chemically and physically) of different hydrogel polymers in an assumed adiabatic condition calorimeter. The different hydrogel polymers vary in the volume of EDMA; 0ml, 0.2ml and 0.6ml. It was determined that the malleability decreases and the structural strength of the hydrogel increase as the amount of EDMA increases. Chemically, the maximum conversion rate and subsequently the rate of product formation both decreases as the amount of EDMA increase. At the end of each trial, about 60 percent of reactants were converted into product proving that no calorimeters in experiments are ideal and adiabatic in nature. The The experimentally developed rate of product formation for trials 1, 2 and 3 are 0.04494 +/- 0.19 M/s, 0.02688 +/0.35 M/s and 0.00966 +/- 0.13 M/s.

I verify that this formal report is my own individual work and has not been copied in whole or in part from another source (with the possible exception of equations, tables and/or diagrams from the experimental descriptions on the APSC100-2 website). Furthermore, I have not and will not lend this report (electronic or hardcopy) to any other student, either now or in the future. Signed:__________________________

1.0 Introduction
The change of heat and temperature of chemical reaction can be measured from a calorimeter. A calorimeter is made of four components: an insulated vessel for the reaction to take place, some form of reactant mixer that initiate/speed up the reaction (ie: Stirrer), a lid to contain the heat and a thermometer that measures the temperature inside the vessel. Enthalpy is the measure of energy absorbed or received by a system. If the system absorbed energy, the enthalpy of a system is positive and the reaction is said to be endothermic (decrease in temperature). In contrast, if the system released energy, the enthalpy of a system is negative and the reaction is said to be exothermic (increase in temperature). There are reactions that have no heat gained or lost by the system. Adiabatic processes occur when the system lost/gained no heat to and from the surrounding. An ideal calorimeter should not lose or gain any heat from outside the reaction vessel; hence any reactions occurring in the vessel are adiabatic in nature. A calorimeter will be used in this experiment to determine the rate of product formation from three radical polymerization reactions. The three reactions involve reacting acrylic acid and EDMA (ethylene glycol dimethacrylate) together to produce a polymer. A polymer is a large molecule composed of repeating structural unit called a monomer (monomer are usually crosslinked with another monomer to form a polymer). Hydrogel is a water insoluble biocompatible polymer used around the world. (Module 2, 61) Hydrogel can be found in disposable diapers, contact lenses, and on the forefront of medical science such as repairing human tissues. (Society for biomaterial) As mentioned before, one monomer crosslink with another to form a polymer. In this experiment, EDMA is used to crosslink the monomer chains of acrylic acid to form the polymer polyacrylic acid as Figure 1: A section of the polyacrylic acid repeating shown in figure 1. Free radical polymerization was chain used to form the polyacrylic acid by using a initiator to break the pre-existing bonds on the monomer Courtesy of Petrucci General Chemistry molecule so other monomers can attach itself onto it. (Module 2, page 61-62) This process will happen repeatedly and the molecule will get large, creating a polymer. The initiator in a free radical polymerization as the name may have suggested, is a molecule with unpaired electrons called a radical. (Module 2, page 61-62) In this lab, hydroxyl radical was used as the initiator. Hydroxyl radical originate from hydrogen peroxide undergoing an oxidation reduction reaction. EDMA is the important crosslink that determines the outcome of the polymer. The amount of EDMA available is directly related to the amount of bonds formed, size of the molecule and affects the properties of the polymer.

In the experiment, the calorimeter is presumed to be adiabetic in nature. This leads us to assume that:

We assume that the overall change enthalpy of the system and heat entering/exiting the system is zero. In addition bonds are form and broken during the reaction known as the enthalpy of reaction and the temperature will increase because this is an adiabatic equation. The enthalpy of the system can be expressed as the enthalpy of polymerization and the enthalpy of the rise in temperature. (Module2, 63)

Since the enthalpy of system equals to zero;

The enthalpy of temperature rise can be obtained by measuring the change in temperature in an experiment.
) ) ))

The theoretical enthalpy value (as shown in table 1) can also be calculated using the enthalpy of poly/mole and the moles of EDMA and acrylic acid.

EDMA volume (ml) 0.2 0.6 0.0

(J) -9050 -9170 -8990

Table 1: The delta H poly complete values for each unique EDMA volume

2.0 Apparatus and Procedure

The experiment apparatus comprised of multiple steps and is shown in figure 2. Using a 250 ml

Figure 2: The general apparatus of the experiment

Nalgene beaker, NaCl and ascorbic acid (in solid form) are carefully weighted to 0.3 grams of each on a piece of waxed paper sitting on top of a top loading balance. The weighted solids are then deposited into the beaker, followed by then addition of 16.3 ml of water. At the fume hood, 0.2 ml of EDMA (for the first trial) and 7.6 ml of acrylic acid are added to the beaker. Place a piece of parafilm over the most of the top of beaker and proceed to place the nitrogen tube directly into the solution. The purpose of the nitrogen is to eliminate the oxygen from the solution, because oxygen prevents the free radicals from generating and inhibits the reaction. Fully cover the beaker will parafilm, insect the thermometer into the beaker by breaking through the film and place the beaker into the cooler. Establish a control by taking the temperature (at t=0) before the start of the reaction. Carefully, add 3.8 ml of hydrogen peroxide to the syringe provided and add the hydrogen peroxide to the beaker by breaking through the film, the stopwatch should start simultaneously. The temperature of the reaction vessel will be measured at regular time interval of 20 seconds. Stop the timer after the maximum temperature has been reached and the temperature began to drop, thus ending the data recording of this trial. Perform two more trials using the same method as the first trial, only that the volume of EDMA added will change to 0.6 ml for the second trial the 0.0ml trial for the third trial. Be sure to take qualitative observation of the three hydrogels and aware the key differences among the three are a direct result of the change in EDMA volume.

3.0 Results and Analysis

The values of added solid and water are provided in table 2. Trial 1 0.300 0.304 16.3 Trial 2 0.306 0.294 16.3 Trial 3 0.297 0.298 16.3

Ascorbic Acid (g) +/- 0.5g Sodium Chloride (g) +/- 0.5g Water (ml) +/-0.5ml

Table 2: The measure solid and water values for each trial

The maximum conversion rate is obtained by taking the slope of the 3 to 5 points when the

Figure 3: The conversion and time results of trial 1 in a plot

exponential curve is the steepest. Subsequently, the rate of product formation can be obtained by taking the maximum conversion rate and multiplying that by the concentration of the monomer in the initial solution, 4.2mol/L. (Module 2, 64)

The three trials cover a large range of possible EDMA values (0, 0.2, and 0.6) and provided unique data. Trial 1 used 0.2 ml of EDMA and served as a control for the duration of the experiment. The hydrogel from trial 1 is smooth, translucent, malleable, white swirls at random spots and sticky to touch. The conversion and time plot of trial 1 is shown in figure 3. The plot demonstrated a linear (horizontal) movement and that quickly changed into an exponential growth. The rapid formation of free radicals in free radical polymerization reaction allows the reaction to occur rapidly, as one can see from the graph. The S pattern is perfectly normal in an experiment environment because it takes time for the molecules to interact with each other and the reaction will slow down after the reactants are depleting. After performing linear regression on the graph, the maximum conversion rate was determined to be 0.0107 per sec (s^-1). Subsequently, the rate of product formation was 0.04494M/sec.

In trial 2, the 0.6 ml of EDMA was used and the qualitative observations differ from trial one as

Figure 4: The Conversion time plot of trial 2

expected. The hydrogel was white, hard, and rough in texture and uniform throughout. The relationship of time and conversion was plotted and the similar S shape is also present. The maximum rate of conversion was determined to be 0.0064 per sec and the rate of product formation was concluded to be 0.02688M/s.

After investigating an increase in EDMA, it was decided that a trial dedicated to the decrease in EDMA (relative to the control, EDMA=0.2ml) in order to draw any particular conclusion to this experiment. In

Figure 5: The conversion time plot for trial 3

trial three, no EDMA was added to the solution. EDMA act as a cross link that link the many monomer chains in a monomer, it was predicted that this will significantly differ from that of the control. The hydrogel was found to be smooth, viscous, very malleable and sticky. The max conversion rate is 0.0023 per second and the rate of product formation is 0.00966M/sec.

4.0 Discussion
Based on qualitative observations, there are significant differences in the appearance of the three hydrogel. The colour of the hydrogel goes from transparent to white and the malleability decreases as the EDMA increase. The decrease of malleability is a result of the increase in EDMA, which also means an increase in crosslinks. The more crosslinks, the less ways the monomer chains can alter themselves around in terms of location. To confirm this, it was found during the lab that the 0.2 ml EDMA hydrogel broke easier than that of the 0.6ml. The 0.2 ml sample has less cross links than that of the 0.6 ml, and the less cross links it has, the easier it will break because there are less support among the structure of the polymer. In the experiment, the conversion rates only reached 50-60% of full conversion. In fact, no real world experiments can reach the point of 100% because that is a theoretical value and random errors will always limit the conversion rate from reaching 1. The experiment did not have a perfectly adiabatic

calorimeter and some of the energy from the reaction would have been lost to the surrounding. The data show that the reaction converted a mere 60%, suggesting that a significant amount of heat was lost from the system. As mentioned above, no calorimeters in the world are perfectly adiabatic. With that being said, the percentage of heat generated lost to the surrounding will increase. Because there is a proportional relationship with the percentage of heat generated lost to the surrounding and the reaction rate. It is safe to say that as reaction rate increase, the percentage of heat generated lost to the surrounding will also increase. This make sense because the increase in rate reaction means more bonds are made and broken, which in terms create more heat energy. According to the data, the increase in concentration of EDMA appears to decrease the rate of product formation. As mentioned before, increase in EDMA cause the hydrogel to increase in solid like behaviours such as decrease in malleability and increase in the strength of the material.

5.0 Conclusion
This lab aimed to experiment with different compositions of hydrogel polymers and identify any patterns of interest by comparing volume of EDMA each hydrogel have. After concluding the experiment, it has been proven that the three hydrogel does indeed have different chemical and physical properties. As EDMA increase, the hydrogels become more solid like (Malleability goes down and harder to break). Chemically, increases in EDMA decrease the conversion rate in turns decrease the rate of product formation. The experimentally developed rate of product formation for trials 1, 2 and 3 are 0.04494 +/- 0.19 M/s, 0.02688 +/- 0.35 M/s and 0.00966 +/- 0.13 M/s. Because the values were obtained experimentally: the high uncertainty, low conversion rate and the non-perfect adiabatic calorimeter of the values were expected.

6.0 Reference
"Biomaterial of the Month - Hydrogels." Society for Biomaterials. N.p., 1 June 2007. Web. 4 Feb. 2012. <http://www.biomaterials.org/week/bio17.cfm>. Clapham, Lynann. APSC 100 Practical Engineering Module 2. Kingston: Queen's University, 2011. Print.

7.0 Appendix
7.1 Trial 1 data, regression and error calculation

Trial 1 EDMA Volume (ml) +/- 0.5 0.2 ml Water Vol (ml) +/- 0.5 ml 16.3 Acrylic Acid Vol (ml) +/- 0.5 7.6 ml Ascorbic Acid (g) +/0.3 0.0005g t (s) T (C) +/0.5 Celcius 0 20 40 60 80 100 120 140 160 180 200 220 230 240 260 280 Rate of Formation (M/S) 20.6 21.3 21.6 21.9 22.2 22 21.9 21.8 22.4 22.6 28.6 37.6 46 58.2 81.8 84.7 0.04494

T (K) +/- 0.5 Kelvin 293.8 294.5 294.8 295.1 295.4 295.2 295.1 295 295.6 295.8 301.8 310.8 319.2 331.4 355 357.9

T (K) +/- 0.5 Kelvin 0 0.7 1 1.3 1.6 1.4 1.3 1.2 1.8 2 8 17 25.4 37.6 61.2 64.1

H_Temperature Rise (J) 0 60.26489 86.0927 111.9205 137.7483 120.5298 111.9205 103.3112 154.9669 172.1854 688.7416 1463.576 2186.754 3237.085 5268.873 5518.542

Conversion (No Units) 0 0.006659 0.009513 0.012367 0.015221 0.013318 0.012367 0.011416 0.017123 0.019026 0.076104 0.161721 0.24163 0.357689 0.582196 0.609784

H_Poly.complete -9050 (J)

Intercept m

Coefficients Standard Error -2.2024 0.116936 0.010687 0.000491

7.2 Trial 2 data, regression and error calculation

Trial EDMA Volume (ml) +/- 0.5 2 0.6

ml Water Vol (ml) +/- 0.5 ml Acrylic Acid Vol (ml) +/- 0.5 ml Ascorbic Acid (g) +/0.0005g

16.3 7.6 0.306

t (s)

T (C) +/0.5 Celcius 20.9 22.3 22.6 23.1 23.9 25.6 27.8 33.3 43.1 59.8 72.3 77.8 80.4 80.6 0.02688

T (K) +/- 0.5 Kelvin 294.1 295.5 295.8 296.3 297.1 298.8 301 306.5 316.3 333 345.5 351 353.6 353.8

0 20 40 60 80 100 120 140 160 180 200 220 240 260 Rate of Formation (M/S)

T (K) +/- 0.5 Kelvin 0 1.4 1.7 2.2 3 4.7 6.9 12.4 22.2 38.9 51.4 56.9 59.5 59.7

H_Temperature Rise (J) 0 113.2667 137.5382 177.9906 242.7144 380.2526 558.2431 1003.22 1796.087 3147.197 4158.507 4603.483 4813.836 4830.017

Conversion (No Units) 0 0.012352 0.014999 0.01941 0.026468 0.041467 0.060877 0.109402 0.195865 0.343206 0.45349 0.502016 0.524955 0.526719

H_Poly.complete -9170 (J)

Intercept m

Coefficients Standard Error -0.82846 0.096669 0.006441 0.000535

7.3 Trial 3 data, regression and error calculation

Trial EDMA Volume (ml) +/- 0.5 ml Water Vol (ml) +/- 0.5 ml Acrylic Acid Vol (ml) +/- 0.5 ml Ascorbic Acid (g) +/0.0005g 3 0 16.3 7.6 0.297 ( ) )

t (s)

0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460

T (C) +/- 0.5 Celcius 20.8 22.3 22.7 22.8 22.7 22.8 23 23.7 24.4 25.6 27.8 30.8 34.5 38.5 40.8 41.8 44.5 46.1 47.3 50.3 53.1 56.4 60.8 66.2

T (K) +/0.5 Kelvin 294 295.5 295.9 296 295.9 296 296.2 296.9 297.6 298.8 301 304 307.7 311.7 314 315 317.7 319.3 320.5 323.5 326.3 329.6 334 339.4

T (K) +/- 0.5 Kelvin 0 1.5 1.9 2 1.9 2 2.2 2.9 3.6 4.8 7 10 13.7 17.7 20 21 23.7 25.3 26.5 29.5 32.3 35.6 40 45.4

H_Temperature Conversion Rise (J) (No Units) 0 128.53 162.8046 171.3733 162.8046 171.3733 188.5106 248.4913 308.4719 411.2959 599.8065 856.8664 1173.907 1516.654 1713.733 1799.419 2030.773 2167.872 2270.696 2527.756 2767.678 3050.444 3427.466 3890.173 0 0.014297 0.01811 0.019063 0.01811 0.019063 0.020969 0.027641 0.034313 0.04575 0.066719 0.095313 0.130579 0.168705 0.190627 0.200158 0.225892 0.241143 0.25258 0.281174 0.307862 0.339315 0.381253 0.432722

Rate of Formation (M/S)

0.00966 Coefficients -0.6162 0.002273 Standard Error 0.032064 7.12E-05

480 500 520 540

70.5 75.2 76.7 77.1

343.7 348.4 349.9 350.3

49.7 54.4 55.9 56.3

4258.626 4661.353 4789.883 4824.158

0.473707 0.518504 0.532801 0.536614 Intercept m

H_Poly.complete -8990 (J)