Catalytic Reaction Rate Lab

Department of Chemical Engineering and Materials Science University of California Davis

Reactions of t-Butyl Alcohol with Acid Catalysis in Sulfonic Acid Resin!

By

Brett Koehn

For

Professors Gates and Tseregounis

ECH 155: Chemical Engineering Laboratory

Group #1

Ethan Jensen, Chris Gee, and Zheyu Li

Experiment Performed: January 14, 2016

Report Submitted: January 25, 2016

Table of Contents:

Abstract……………………………………………………………………………………………4

Introduction………………………………………………………………………………………..4

            Figure 1……………………………………………………………………………………5

Theory……………………………………………………………………………………………..6

Experimental Methods…………………………………………………………………….………7

            Figure 2……………………………………………………………………………………9

Results…………………………………………………………………………………………....10

            Figure 3…………………………………………………………………………………..11

            Table 1………………………………………………………………………………...…12

Discussion……………………………………………………………………………………..…13

            Figure 4…………………………………………………………………………………..14

Conclusion…………………………………………………………………………………….…15

Nomenclature Table……………………………………………………………………………...15

References………………………………………………………………………………………..16

Appendix A………………………………………………………………………………………17

            Table 2…………………………………………………………………………………...17

            Table 3…………………………………………………………………………………...17

            Table 4…………………………………………………………………………………...17

            Table 5…………………………………………………………………………………...18

            Table 6…………………………………………………………………………………...18

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            Table 10………………………………………………………………………………….21

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            Table 15………………………………………………………………………………….28

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            Table 53………………………………………………………………………………….68

            Table 54………………………………………………………………………………….70

Appendix B………………………………………………………………………………………72

            Figure 5…………………………………………………………………………………..72

Appendix C………………………………………………………………………………………73

            Figure 6…………………………………………………………………………………..73

            Figure 7…………………………………………………………………………………..73

            Figure 8…………………………………………………………………………………..74

            Figure 9…………………………………………………………………………………..75

            Figure 10…………………………………………………………………………………75

            Figure 11…………………………………………………………………………………75

            Figure 12…………………………………………………………………………………76

            Figure 13…………………………………………………………………………………76

            Figure 14…………………………………………………………………………………77

            Figure 15…………………………………………………………………………………77

            Figure 16…………………………………………………………………………………78

            Figure 17…………………………………………………………………………………78

            Figure 18…………………………………………………………………………………79

Abstract:

            During this experiment, we analyzed the formation of isobutylene (IB) gas. This was created through a dehydration reaction involving t-butyl alcohol (TBA) and sulfonic acid as a catalyst. We were able to measure the formation of IB by creating bubbles in a buret, and measuring the volume traveled and time elapsed of these IB bubbles. We also measured the pressure of the room, the temperatures inside the reactor and of the room, and the volumes of solution which filled the reactor, which contained varieties TBA, water, and MCH. We also did a titration in order to determine the number of moles of NaOH required to occupy the active sites of sulfonic catalyst. This number of moles allowed us to find the equivalent active sites of catalyst per 1 gram of catalyst. This allowed us to calculate the rate at which IB was formed based off of a variety of changing parameters.

Introduction:

            Catalysts have important applications with respect to quality control, environmental safety, and pollution control. In industrial applications, catalysts are used to purify chemical reactants and products. This purification can stop the formation of harmful side products and help the creation of the useful products. An example of this (1), is using the catalyst sulfonated poly(styrene-divineylbenzene) to purify methanol and IB. These compounds are then used to create methyl-t-butyl (MTBE) and TBA, which are also purified with catalyst. Finally, MTBE and TBA are reacted with tetraethyl lead to form very high octane content gasoline. Furthermore, IB is a major compound used in the petroleum industry (2). However, IB is commonly contaminated with paraffins. IB can be purified by reacting olefins with water to give TBA. TBA and the parrafins can easily be separated because they have different molecular weights. The pure TBA is then reconverted back to very pure IB by catalytic dehydration, which most commonly involves the ion-exchange resin catalyst containing sulfonic acid groups. This process is very similar to what we performed in laboratory.

            The dehydration reaction we performed in this reactor laboratory is shown below (3).

Figure 1: The dehydration of TBA by sulfonic acid catalyst to yield IB.

First, the alcohol group of TBA protonates a hydrogen from sulfonic acid group of the catalyst. This creates the leaving group of water. As water leaves from TBA, another hydrogen dissociates from a methyl group of TBA, which creates a double bond and in turn, the molecule of IB. The dissociated hydrogen is then ready to attach to another TBA alcohol group, and the whole process repeats.

            The alcohol group of TBA, pKa≈17 (4), is able to protonate the sulfonic acid, pKa≈-2.6, because the pH of TBA is much greater. The water molecule attached to TBA is then able to leave because water is a good enough leaving group. However, a carbocation which has an electron deficient central carbon is unstable. Therefore, an adjacent carbon will sacrifice a hydrogen simultaneously to create a double bond between the adjacent carbon and center carbon. The IB molecule is then stabilized.

Theory:

Theory is that the formation of IB is dependent on the amount of catalyst, temperature inside the reactor, and concentrations of TBA, IB, and water (5). Therefore, careful measurements of each of these parameters is important. The collection of catalyst masses and reactor temperature measurements are straightforward, and can be recorded by a mass balance and thermocouple respectively. The difficult parameters to measure are the concentrations of TBA, IB, and water. The initial concentrations of the solutions is known because we created the solutions with specific volumes of TBA, water, and MCH. Furthermore, we know the molecular weights and densities (at room temperature) of all these compounds. Aspen plus is used to estimate what the densities will be in the reactor during the experiment. The equations for calculating concentration are shown below

where C is the concentration of any component of a solution in moles per liter, ρ is the density in grams per milliliter, MM is the molecular mass in grams per mole, V is volume in liters, n is the number of moles, P is pressure in atmospheres, R is the gas constant in kilocalories per degree Kelvin and mole, and T is temperature in degrees Kelvin.

where F_IB is the flow rate of IB in milliliters per second, ΔV is the change of volume in milliliters, and Δt is the change of time in seconds.

            IB must be assumed to be ideal in order to use the ideal gas law. This allows us to convert the measured output parameter of milliliters per second of IB to the more useful units of mole per second of IB. We also assume the IB exiting the reactor in the buret to be at room temperature, and therefore we calculate the molar volume of our ideal gas IB.

where R_IB is the formation of IB in moles of IB per equivalent moles of catalyst m_c is the mass of catalyst in grams, X_c is the conversion of moles of sulfonic acid per gram of catalyst, R is the gas constant in kcal per mole and degree centigrade, T_N is the normalized temperature of 353 kelvin, and T_RXN is the temperature inside the reactor. X_c is found by performing a mole balance on the NaOH consumed during a titration of catalyst. The number of moles of NaOH is equivalent to the moles of sulfonic acid per gram of catalyst.

            The literature (6) by Gates and Rodriguez supplies a set of experimental data for the reaction rate as a function of the combined concentrations of TBA and water or TBA and MCH. Therefore, we have a basis of expected exiting flow rates of IB relative to the initial concentrations of TBA, water, and MCH. The spreadsheet lists the different solutions and their concentrations we will prepare during this laboratory experiment. We will then compare our measured exiting flowrates of IB with the literatures predictions. If the flowrate data is within 10% of the literature prediction we will accept the data.

Experimental Methods:

            We began our experiment by weighing out 20 catalyst samples, which ranged from masses of 1 to 10 grams. We then dried these samples in a vacuum oven overnight at a temperature of 393 K. We then returned the next morning to create mixtures of pure TBA, TBA and water, and TBA with MCH. We used figure 2 from Gates and Rodriguez, 1973, as a basis for choosing what mixtures to make of TBA and water. We wanted to be able to fit the curve sufficiently in figure 2.

            Once a mixture was prepared, we clean the reactor with that respective mixture. For example, if we were running a trial of TBA with MCH, we first cleaned out the reactor with a mixture of the same concentration TBA with MCH in order to stop contamination. We then placed the majority of the mixture in the reactor, and brought the reactor to reflux. Next, we quickly transferred the dried catalyst to the reactor, washed the catalyst down with the remaining respective mixture, and capped the reactor. The stop watch was started once the catalyst was removed from the oven. During each trial, we measured the temperature within the reactor constantly. Once there was IB exiting the reactor into the buret, we created soap bubbles and measured the time it took each bubble to travel specific volumes within the buret. After we had enough data to establish the initial exiting flow rate of IB, we added water to slow down the reaction. Finally, we disposed of the reactant mixture in the labeled waste disposal container. We did the same for the catalyst.

             We also did a titration during this laboratory experiment. We soaked 1 gram of catalyst with 200 mL of .1-M NaOH, which included 5% (by weight) NaCl. We let this catalyst soak overnight, we back titrated 50 mL aliquots of the supernatants, which was the solution without the catalyst. The indicator used was .1 M HCl with phenolphthalein. This indicator turned from pink to clear once the titration was complete. The volume of .1 HCl was used to find the moles of NaOH remaining. The moles of NaOH remaining was subtracted from the original moles of NaOH to find the moles of NaOH used in the titration. This allowed us to find the moles of active sites of SO3H sites per gram of catalyst.

Figure 2: The Semi-batch reactor attach to a thermos couple and buret.

            We calculated the concertation of IB leaving with the ideal gas law. We then calculated the reaction rate of IB with the concentration of IB, weight of catalyst, and exiting flow rate. This rate was converted by the number of active sites of SO3H sites per gram of catalyst to give the more useful units of (moles of IB produced)/ (moles of catalyst –SO3H groups).

            The spreadsheet and table we created by extracting data from Gates and Rodriguez. This spreadsheet contained the moles need the make 200 mL mixtures of TBA, water, and MCH. However, we scaled this up to 225 mL, so we would have enough solution to clean the reactor and wash down catalyst. We multiplied the desired TBA concentration by 225 mL to find the moles of TBA. This is then multiplied by the molar volume to of TBA to calculate the total volume. The predicted IB exiting was calculated with the ideal gas law. We used the pressure of the Sacramento airport, R constant, and room temperature. We calculated the moles of equivalent SO3H groups by multiplying the mass of catalyst by the ratio in Gates and Rodriguez. We calculated the theoretical IB flow rate with reaction rate from Gates and Rodriguez and multiplying this rate by the number of moles of equivalent SO3H groups. We then divided this by the molar volume of IB.

            We then plotted the reaction rates versus the concentration of reagent. This allowed us to find the initial reaction rate. This plot also allowed us to examine the influence of concentration on reaction rate. We then used a least squares approach to determine the best non-linear fit of equation 1. We varied k, Ka, and Kw, which ranged from values of 0 to 3.

            During different trials, we varied the stirring, catalyst’s mass, reactor temperature, room temperature, and the concentrations of TBA, water, and MCH to determine how these parameters affected the reaction rate. We also did trials without varying anything to check if the reaction rates were reproducible. These variations allowed us to perform error analysis on our data.

Results:

            We began analyzing the results by compiling all of our data into excel. We converted stopwatch stylized times with units of minutes and seconds to units of just seconds. Next, we calculated the average time between the start and end times. We also took difference of the start and ends to get the bubble motion time. We then obtained the flow rate in milliliters per second from dividing the volume traveled of the IB bubble by the bubble motion time. The highest flow rate we obtained was 12.5±2.5 milliliters per second and occurred during an experiment with no stirring of pure TBA solution. The lowest flow rate we obtained rate recorded was .385±.077 milliliters per second and occurred during the experiment with highest concentration of water.

            We plotted the IB exiting flow rate as a function of the average bubble occurrence time in excel. The data, which occurred after the peak flow rate, was then fitted linearly. The y-axis intercept of this fit was our initial exiting flow rate of IB. We converted the flow rate of IB to evolution rate of IB in units of moles per equivalent acid groups per seconds by using the ideal gas law, relationship between moles of equivalent acidic groups per grams of catalyst, and the Arrhenius equation.

Figure 3: The least squares fit of our experimental data with raw data from Gates and our experiment. The values of our experimental this data can be found in table 1.

            The initial formation reaction rates in units of moles of IB produced per equivalent acid groups per seconds were then plotted as function of concentration of TBA. This plot was fitted by performing a non-linear least squares fit in Matlab. This plot was superimposed and compared to the data from Gates and Rodriguez.

Table 1: The Formation Rate of IB for each trial.

Trial	rIB [moles of IB/equiv moles SO3H*s]
Pure TBA	.0374±.0075
Pure TBA Repeat	.0366±.0073
Pure Tba No Stirring	.00329±.0066
Pure TBA High Catalyst	.0237±.047
Water 1	.000381±7.6E-5
Water 2	.00131±.00026
Water 3	.00390±.00078
Water 4	.0157±.0031
Water 5	.0306±.0061
MCH 1	.00926±.0027
MCH 2	.0202±.0040
MCH 3	.0246±.0049

The error in the concentration data is calculated from the error in the density, molecular weight, and temperature within the reactor. However, the error in molecular weight and temperature were disregarded, because both are negligible compared to the error in density. The error in density is then estimated to be 10%, because we used aspen to calculate the densities at 80 degrees centigrade. Aspen gave theoretical densities and not experimental densities, therefore there is no way to calculate error from Aspen and an estimation has to be made. Furthermore, this error increased to 20% in mixed solutions, because there is an uncertainty each component of the solutions.

            The error in reaction rate is calculated several ways, and the highest percent error is used. The first method is combining the error for every measurement we made. The measurements involved were the volume traveled by the bubble, the time elapsed by the bubble, and the pressure and temperature of the room. The pressure and temperature of the room are negligible. We also assumed the gas was ideal, but the error in this assumption is negligible. Therefore the error is only dependent on the volume traveled by the bubble, and the time elapsed by the bubble. Since these two measurements were related, we assumed the errors were the same. Therefore, we equated the error in time elapsed to the error in volume traveled. The error in volume traveled was estimated to be 10% of each respective measurement. This error was then doubled because of the additional error due to uncertainty in time.

            The second method for calculating error in reaction rate was plotting three linear fits for the initial flow rate of IB. The two outer fits were taken to be the range of error in flow, which were converted to a range of error in reaction rate.

            The third method for calculating error in reaction rate came from using Matlab to perform a fit with a non-linear least squares errors technique. Matlab uses this technique to report an error relative to the sum of all the reaction rates. The equation that fit the best for water was

where R_IB is the formation rate of IB,  is the concentration of TBA, C_w is the concentration of water which if found from the concentration of TBA, and κ, κ’, K_A, K_w, are the reaction rate constants we found. The reaction rate constants were .11 , -1.1E-4 .054, and 1.9 respectively.

Where the water concentration term is removed from this equation because there was not water during these trials. The values of κ, κ’, K_A for the MCH trials were .04 moles/((equiv acids)*s), .002 moles/((equiv acids*s)), and.09  L/moles acid respectively.

Discussion:

First off, we threw away the MCH 3 redo trial, which had solution that was 25% MCH by concentration, because it did not fit the data well. This was our last trial performed, and thus we committed the most error in performing this trial. For this trial, we did not transfer the catalyst smoothly, nor did we take concise measurements of the bubbles.

Figure 3 shows the presence of additional components has varying effects on the formation of IB. Water is an inhibitor during this reaction. Therefore water inhibits both the catalyst and TBA, which slows down formation of IB tremendously. Water only exhibits similar formation rates of MCH, an inert, at low concentrations such as 2% and .5%. MCH barely affects the formation rate. This inert slightly slows down the rate because this inert is taking up space of TBA, and therefore there is not as much TBA to turn into IB.

Figure 4: My proposed process for purifying IB and TBA in industry. A hydrocarbon stream is fed in and purified by Diol. This stream of TBA is then heated and treated with sulfonic catalysts to produce IB. The catalyst and TBA are then disposed of.

            Water would also slow down industrial processes, such as the synthesis of MTBE or the hydration of propylene. This is because water would inhibit propylene, MTBE, and the catalyst.

The limiting case of this experiment is the amount of water in solution. We used large amounts of catalyst for the high concentration water solutions, and we recorded the slowest IB formation rates. Furthermore, we performed two trials with pure TBA solution and no stirring. In one of these trials we used 4 grams of catalyst, and for the other we used 1 gram of catalyst. The trial with 1 gram of catalyst exhibited a higher flow rate. Therefore, the amount of catalyst is not the limiting case, unless we were to use less than 1 g of catalyst.

Equation 4 further proves water as the limiting factor in this process because the least squares fit worked best with an exponent of 2 on the water dependent term. This shows that waters inhibition was so important that the term had to be squared in order to provide the proper fit.

We chose the highest error values that were calculated for each reported formation rate of IB. Therefore, we gave the highest range of error possible, which is the responsible choice.

The data agrees with the general trend from literature, however there ae some discrepancies. The best fit lines agree with the error in concentration measurements, but not with all the error in the rate measurements. Some of the rate measurements do not have error which includes the best fit lines, because we estimated the error of these rates, and we considered many factors negligible. Also, the some rates were small, so 20% error ranges were almost insignificant. Therefore, some rate error ranges did not encompass the best fit lines.

Conclusion:

            We found that the dehydration of TBA with a sulfonic acid to produce IB is a reaction that depends on a plethora of parameters. However, the most important parameter was the concentration of the solution containing TBA. Specifically, the rate of formation of IB was greatly dependent on if this solution of TBA was pure, mixed with an inert (MCH), or an inhibitor (water). Pure TBA and solutions mixed with an inert reacted faster than solutions containing inhibitors. This is because inhibition slows down the dehydration of TBA, and therefore limits the formation of IB.

Nomenclature Table:

Table 2: Nomenclature Table

C	Concentration	mole/L
CA	Concentration of TBA	mole/L
Cw	Concentration of Water	mole/L
FIB	Flow rate of IB	mL/s
IB	Isobutylene	none
κ	Reaction Rate Constant	moles/(equiv acidic groups*s)
κ’	Pseudo-First-Order Rate Constant	L/(equiv acidic groups*s)
KA	TBA Rate Constant	L/moles
Kw	Water Rate Constant	L/moles
MCH	Methylcyclohexane	none
MM	Molecular Mass	g/moles
ρ	Density	g/mL
P	Pressure	Atm
R	Gas Constant	kCal/(K*moles)
RIB	Rate Formation of IB	moles of IB/moles of catalyst
T	Temperature	K
TN	Normalized Temperature	K
TRXN	Reactor Temperature	K
TBA	t-butyl alcohol	none
Δt	Elapsed Bubble Time	s
V	Volume	L
ΔV	Volume Traveled by Bubble	mL
Xc	Conversion Factor of Active Catalyst	moles/g

Refrences:

1.      Olah, G. A, “Hydrocarbon Chemistry”, Wiley-Interscience, Molnar, Arpad, ISBN 978-0-471-41782-8.

2.      Balaban, A.T., “Leaded Gas Phaseout”, U.S. EPA, Region 10. June 1995.

3.      Schore, N. E., Vollhardt, K. P. C., “Organic Chemistry, Structure and Function”, W. H. Freeman and Company, New York, 2007 (262-264).

4.      Evans, “pKa Table”, Bordwell, ACR, 1988, http://evans.rc.fas.harvard.edu/pdf/evans_pKa_table.pdf, http://www.chem.wisc.edu/areas/reich/pkatable/index.htm

5.      Tseregounis, S., Gates, J. B., “Kintetic of Catalytic Dehydration of t-Butyl Alcohol In A Semi-Batch Reactor”, University of California, Davis, Dept of Chemical Engineering and Materials Science, Winter 2016.

6.      *Gates, B. C.; Rodriguez, W., J., “General and Specific Acid Catalysis in Sulfonic Acid Resin”, Journal of Catalysis 31, 27-31 (1973).

Appendix A: Raw Data

Table 3: Non-linear Least Squares Fit Rate Coefficients for water and MCH respectively.

Parameter	Value	Units
κ	0.1076	moles/(equiv acidic groups*s)
KA	0.0538	L/moles
Kw	1.9085	L/moles
κ’	-1.11E-04	L/(equiv acidic groups*s)
κ	0.0403	moles/(equiv acidic groups*s)
KA	0.0893	L/moles
κ’	0.0018	L/(equiv acidic groups*s)

Table 4: Titration Data

Catalyst mass [g]	0.1 N NaOH in 5% wt NaCl [mL]
1	200
Aliquot1 [mL]		Aliquot2 [mL]	Aliquot3 [mL]
50		50	50
0.1 N HCl 1 [mL]		0.1 N HCl 2 [mL]	0.1 N HCl 3 [mL]
40.4		38.4	38.9
Moles HCl Used 1 [mol]		Moles HCl Used 2 [mol]	Moles HCl Used 3 [mol]
0.00404		0.00384	0.00389
NaOH neutralized 1 [mol]		NaOH neutralized 2 [mol]	NaOH neutralized 3 [mol]
0.00404		0.00384	0.00389
Original NaOH 1 [mol]		Original NaOH 2 [mol]	Original NaOH 3 [mol]
0.005		0.005	0.005
NaOH lost to SO3H 1 [mol]		NaOH lost to SO3H 2 [mol]	NaOH lost to SO3H 3 [mol]
0.00096		0.00116	0.00111
Mol SO3H per gram catalyst 1 [mol/g]		Mol SO3H per gram catalyst 2 [mol/g]	Mol SO3H per gram catalyst 3 [mol/g]
0.00384		0.00464	0.00444

Table 5: Pure TBA Data Part A

cA [mol/L]	cW [mol/L]	cMCH [mol/L]	P [atm]	T [K]	R
10	0	0	1.007987701	296.31	82.06
Volume A [mL]	Volume W [mL]	Volume MCH [mL]
200	0	0
Gates rate [mol/equiv acid groups *s]	n/V=P/RT	Predicted IB flow rate [mL/s]	Expt IB flow rate [mL/s]	Expt rate [mol/equiv acid groups*s]	Yellow color indicates value will be changed to reflect conditions during experiment
0.028	4.1455E-05	2.026291274	4.6739	0.037401132
			5.5	0.044011688
			3.8478	0.030790577
				0.006610556

Table 6: Pure TBA Data Part B

Catalyst mass [g]	Catalyst moles SO3H	Gates moles SO3H/g catalyst	Expt moles SO3H/g catalyst
1	3.00E-03	3.00E-03	0.004306667
T reactor [K]
355

Table 7: Pure TBA Data Part C

Column1	Column2	Column3	Column4	Column5	Column6	Column7	Column8
IB Buret Volume Bubble Travel [mL]	Bubble Motion Time [s]	Start	End	Start [s]	End [s]	Average of Start and End [s]	Flow Rate [mL/s]
50	18	0:47	1:05	47	65	56	2.77777778
50	12	1:14	1:26	74	86	80	4.16666667
50	10	1:36	1:46	96	106	101	5
50	10	1:50	2:00	110	120	115	5
50	12	2:06	2:18	126	138	132	4.16666667
50	11	2:20	2:31	140	151	146	4.54545455
50	11	2:34	2:45	154	165	160	4.54545455
50	11	2:48	2:59	168	179	174	4.54545455
50	10	3:02	3:12	182	192	187	5
50	13	3:15	3:28	195	208	202	3.84615385
50	14	3:30	3:44	210	224	217	3.57142857
50	14	3:44	3:58	224	238	231	3.57142857
50	14	3:59	4:13	239	253	246	3.57142857
50	14	4:13	4:27	253	267	260	3.57142857
50	14	4:27	4:41	267	281	274	3.57142857
50	13	4:42	4:55	282	295	289	3.84615385
50	12	4:58	5:10	298	310	304	4.16666667
50	12	5:13	5:25	313	325	319	4.16666667
50	13	5:31	5:44	331	344	338	3.84615385
50	13	5:59	6:12	359	372	366	3.84615385
50	14	6:16	6:30	376	390	383	3.57142857
50	14	6:33	6:47	393	407	400	3.57142857
50	14	6:54	7:08	414	428	421	3.57142857
50	14	7:13	7:27	433	447	440	3.57142857
50	14	8:07	8:21	487	501	494	3.57142857
50	15	8:25	8:40	505	520	513	3.33333333

Table 8: Pure TBA Repeat Data A

Column1	Column2	Column3	Column4	Column5	Column6
cA [mol/L]	cW [mol/L]	cMCH [mol/L]	P [atm]	T [K]	R
10	0	0	1.00631663	296.22	82.06
Volume A [mL]	Volume W [mL]	Volume MCH [mL]
200	0	0
Gates rate [mol/equiv acid groups *s]	n/V=P/RT	Predicted IB flow rate [mL/s]	Expt IB flow rate [mL/s]	Expt rate [mol/equiv acid groups*s]	Yellow color indicates value will be changed to reflect conditions during experiment
0.028	4.13989E-05	2.039184807	4.6023	0.03659532
			5	0.039757643
			4.2	0.03339642
				0.003162323

Table 9: Pure TBA Repeat Data B

Column1	Column2	Column3	Column4
Catalyst mass [g]	Catalyst moles SO3H	Gates moles SO3H/g catalyst	Expt moles SO3H/g catalyst
1.005	3.02E-03	3.00E-03	0.00430667
T reactor [K]
355

Table 10: Pure TBA Repeat Data C

Column1	Column2	Column3	Column4	Column5	Column6	Column7	Column8
IB Buret Volume Bubble Travel [mL]	Bubble Motion Time [s]	Start	End	Start [s]	End [s]	Average of Start and End [s]	Flow Rate [mL/s]
50	13	0:47	1:00	47	60	54	3.85
50	11	1:04	1:15	64	75	70	4.55
50	13	1:20	1:33	80	93	87	3.85
50	12	1:36	1:48	96	108	102	4.17
50	12	1:51	2:03	111	123	117	4.17
50	13	2:12	2:25	132	145	139	3.85
50	12	2:28	2:40	148	160	154	4.17
50	12	2:45	2:57	165	177	171	4.17
50	11	3:03	3:14	183	194	189	4.55
50	13	3:21	3:34	201	214	208	3.85
50	11	3:40	3:51	220	231	226	4.55
50	12	4:04	4:16	244	256	250	4.17
50	13	4:22	4:35	262	275	269	3.85
50	13	4:40	4:53	280	293	287	3.85
50	14	4:58	5:12	298	312	305	3.57
50	14	5:16	5:30	316	330	323	3.57
50	14	5:34	5:48	334	348	341	3.57
50	12	5:51	6:03	351	363	357	4.17
50	13	6:07	6:20	367	380	374	3.85
50	14	6:23	6:37	383	397	390	3.57
50	13	6:40	6:53	400	413	407	3.85
50	13	6:56	7:09	416	429	423	3.85
50	14	7:13	7:27	433	447	440	3.57
50	15	8:26	8:41	506	521	514	3.33
50	16	9:42	9:58	582	598	590	3.13

Table 11: Pure TBA No Stirring Data A

Column1	Column2	Column3	Column4	Column5	Column6
cA [mol/L]	cW [mol/L]	cMCH [mol/L]	P [atm]	T [K]	R
10	0	0	1.00899034	296.55	82.06
Volume A [mL]	Volume W [mL]	Volume MCH [mL]
200	0	0
Gates rate [mol/equiv acid groups *s]	n/V=P/RT	Predicted IB flow rate [mL/s]	Expt IB flow rate [mL/s]	Expt rate [mol/equiv acid groups*s]	Yellow color indicates value will be changed to reflect conditions during experiment
0.028	4.14627E-05	2.042124663	4.1422	0.032889406
			4.5	0.035730367
			3.7844	0.030048444
				0.002840961

Table 12: Pure TBA No Stirring Data B

Column1	Column2	Column3	Column4
Catalyst mass [g]	Catalyst moles SO3H	Gates moles SO3H/g catalyst	Expt moles SO3H/g catalyst
1.008	3.02E-03	3.00E-03	0.00430667
T reactor [K]
355

Table 13: Pure TBA No Stirring Data C

Column1	Column2	Column3	Column4	Column5	Column6	Column7	Column8
IB Buret Volume Bubble Travel [mL]	Bubble Motion Time [s]	Start	End	Start [s]	End [s]	Average of Start and End [s]	Flow Rate [mL/s]
50	17	0:22	0:39	22	39	30.50	2.94117647
50	14	0:47	1:01	47	61	54.00	3.57142857
50	15	1:05	1:20	65	80	72.50	3.33333333
50	13	1:23	1:36	83	96	89.50	3.84615385
50	15	1:45	2:00	105	120	112.50	3.33333333
50	15	2:04	2:19	124	139	131.50	3.33333333
50	15	2:21	2:36	141	156	148.50	3.33333333
50	14	2:40	2:54	160	174	167.00	3.57142857
50	19	2:52	3:11	172	191	181.50	2.63157895
50	14	3:19	3:33	199	213	206.00	3.57142857
50	14	3:37	3:51	217	231	224.00	3.57142857
50	14	3:55	4:09	235	249	242.00	3.57142857
50	15	4:13	4:28	253	268	260.50	3.33333333
50	14	5:20	5:34	320	334	327.00	3.57142857
50	15	5:38	5:53	338	353	345.50	3.33333333
50	15	6:02	6:17	362	377	369.50	3.33333333
50	15	6:21	6:36	381	396	388.50	3.33333333
50	15	6:40	6:55	400	415	407.50	3.33333333
50	16	6:58	7:14	418	434	426.00	3.125
50	15	7:17	7:32	437	452	444.50	3.33333333
50	15	7:36	7:51	456	471	463.50	3.33333333
50	15	7:54	8:09	474	489	481.50	3.33333333
50	15	8:14	8:29	494	509	501.50	3.33333333
50	16	8:32	8:48	512	528	520.00	3.125
50	17	8:51	9:08	531	548	539.50	2.94117647
50	16	9:15	9:31	555	571	563.00	3.125
50	18	10:44	11:02	644	662	653.00	2.77777778
50	20	11:59	12:19	719	739	729.00	2.5
50	19	12:56	13:15	776	795	785.50	2.63157895

Table 14: Pure TBA No Stirring High Catalyst Data A

Column1	Column2	Column3	Column4	Column5	Column6
cA [mol/L]	cW [mol/L]	cMCH [mol/L]	P [atm]	T [K]	R
10	0	0	1.00564821	296.38	82.06
Volume A [mL]	Volume W [mL]	Volume MCH [mL]
200	0	0
Gates rate [mol/equiv acid groups *s]	n/V=P/RT	Predicted IB flow rate [mL/s]	Expt IB flow rate [mL/s]	Expt rate [mol/equiv acid groups*s]	Yellow color indicates value will be changed to reflect conditions during experiment
0.028	4.13491E-05	8.142191671	11.925	0.023747849
			14	0.027880074
			9.85	0.019615624
				0.004132225

Table 15: Pure TBA No Stirring High Catalyst Data B

Column1	Column2	Column3	Column4
Catalyst mass [g]	Catalyst moles SO3H	Gates moles SO3H/g catalyst	Expt moles SO3H/g catalyst
4.008	1.20E-02	3.00E-03	0.00430667
T reactor [K]
355

Table 16: Pure TBA No Stirring High Catalyst Data C

Column1	Column2	Column3	Column4	Column5	Column6	Column7	Column8
IB Buret Volume Bubble Travel [mL]	Bubble Motion Time [s]	Start	End	Start [s]	End [s]	Average of Start and End [s]	Flow Rate [mL/s]
50	5	0:27	0:32	27.00	32	29.50	10
50	4	0:34	0:38	34.00	38	36.00	12.5
50	4	0:43	0:47	43.00	47	45.00	12.5
50	4	1:38	1:42	98.00	102	100.00	12.5
50	5	1:44	1:49	104.00	109	106.50	10
50	5	1:51	1:56	111.00	116	113.50	10
50	4	1:58	2:02	118.00	122	120.00	12.5
50	4	2:05	2:09	125	129	127.00	12.5
50	5	2:11	2:16	131	136	133.50	10
50	4	2:18	2:22	138	142	140.00	12.5
50	4	2:25	2:29	145	149	147.00	12.5
50	5	2:31	2:36	151	156	153.50	10
50	5	2:42	2:47	162	167	164.50	10
50	4	2:50	2:54	170	174	172.00	12.5
50	5	3:00	3:05	180	185	182.50	10
50	4	3:08	3:12	188	192	190.00	12.5
50	5	3:14	3:19	194	199	196.50	10
50	5	3:21	3:26	201	206	203.50	10
50	5	3:38	3:43	218	223	220.50	10
50	4	3:46	3:50	226	230	228.00	12.5
50	5	3:59	4:04	239	244	241.50	10
50	6	4:24	4:30	264	270	267.00	8.33333333
50	5	4:32	4:37	272	277	274.50	10
50	5	4:40	4:45	280	285	282.50	10
50	5	4:48	4:53	288	293	290.50	10
50	6	4:55	5:01	295	301	298.00	8.33333333
50	5	5:04	5:09	304	309	306.50	10
50	5	5:20	5:25	320	325	322.50	10
50	6	5:29	5:35	329	335	332.00	8.33333333
50	6	5:41	5:47	341	347	344.00	8.33333333
50	6	6:00	6:06	360	366	363.00	8.33333333
50	6	6:10	6:16	370	376	373.00	8.33333333
50	6	6:24	6:30	384	390	387.00	8.33333333
50	6	6:43	6:49	403	409	406.00	8.33333333
50	7	6:55	7:02	415	422	418.50	7.14285714
50	6	7:05	7:11	425	431	428.00	8.33333333
50	5	7:36	7:41	456	461	458.50	10
50	6	7:50	7:56	470	476	473.00	8.33333333
50	6	8:01	8:07	481	487	484.00	8.33333333
50	7	8:11	8:18	491	498	494.50	7.14285714
50	7	8:22	8:29	502	509	505.50	7.14285714
50	7	8:33	8:40	513	520	516.50	7.14285714
50	7	8:44	8:51	524	531	527.50	7.14285714
50	7	8:54	9:01	534	541	537.50	7.14285714
50	7	9:05	9:12	545	552	548.50	7.14285714
50	8	9:16	9:24	556	564	560.00	6.25
50	7	9:27	9:34	567	574	570.50	7.14285714
50	7	9:38	9:45	578	585	581.50	7.14285714
50	8	9:49	9:57	589	597	593.00	6.25
50	7	10:01	10:08	601	608	604.50	7.14285714
50	9	11:41	11:50	701	710	705.50	5.55555556
50	9	11:57	12:06	717	726	721.50	5.55555556
50	8	12:10	12:18	730	738	734.00	6.25
50	8	12:22	12:30	742	750	746.00	6.25
50	11	13:13	13:24	793	804	798.50	4.54545455
50	10	13:53	14:03	833	843	838.00	5
50	10	14:43	14:53	883	893	888.00	5

Table 17: Water 1 Data A

Column1	Column2	Column3	Column4
Catalyst mass [g]	Catalyst moles SO3H	Gates moles SO3H/g catalyst	Expt moles SO3H/g catalyst
1.005	3.02E-03	3.00E-0	0.00430667
T reactor [K]
355