## Vapor-Liquid Equilibria and **Physical Property Measurements for 5-Chloromethyl Furfural and**  **Ethyl 5-Methyl-2-Furanoate**

Rubin J McDougal Louis V Jasperson David M VonNiederhausern

Wiltec Research Company, Inc. 488 S 500 W Provo, UT 84601

December 11, 2013

Project Sponsor: xF Technologies Albuquerque, New Mexico

Project Supervisors: Aviad Cahana & Luzheng Zhang xF Technologies Albuquerque, New Mexico

Purchase Order Number:

????i **Abstract**

Binary PTx measurements were performed on the 5-chlorometh yl furfural (CMF) and ethyl 5-methyl-2- furanoate (EMF) system at 80 and 110°C. Data were corr elated with the NRTL Activity Coefficient Model.

Vapor pressure measurements were performed on CMF and EMF. Results wer e correlated with the Antoine Equation.

Liquid heat capacity measurements were performed on CMF and EM F. Results were correlated using a linear fit of the form C = A + BT.

The CMF supplied by xF Technologies had a very short shelf-l ife. Multiple batches were used to complete the measurement program.ii **Table of Contents**

Abstract .................................................................................................................................................................... i
Table of Contents .................................................................................................................................................... ii
List of Tables ........................................................................................................................................................... iii List of Figures ..........................................................................................................................................................iv
Introduction ............................................................................................................................................................ 1
Results and Discussion ............................................................................................................................................ 2 Apparatus and Procedures ...................................................................................................................................... 3
Data Reduction ........................................................................................................................................................ 5 Acknowledgments ................................................................................................................................................... 8
Tables ...................................................................................................................................................................... 9 Figures ................................................................................................................................................................... 16iii **List of Tables**

Table 1. PTx Measurement Results for Ethyl 5-Methyl-2-Fur anoate + 5-Chloromethyl Furfural at 80°C ............. 9 Table 2. PTx Measurement Results for Ethyl 5-Methyl-2-Fur anoate + 5-Chloromethyl Furfural at 110°C ......... 10 Table 3. Vapor Pressure Measurements for 5-Chloromethyl Fu rfural ................................................................ 11 Table 4. Vapor Pressure Measurements for Ethyl 5-Methyl-2- Furanoate ........................................................... 12 Table 5. Heat Capacity of 5-Chloromethyl Furfural an d Ethyl 5-Methyl-2-Furanoate ......................................... 13
Table 6. Source and CAS Numbers of Chemicals .................................................................................................. 14 Table 7. Physical Properties of Chemicals ............................................................................................................ 15iv **List of Figures**

Figure 1. PTx Plot for Ethyl 5-Methyl-2-Furanoate + 5-C hloromethyl Furfural at 80°C ....................................... 16 Figure 2. PTx Plot for Ethyl 5-Methyl-2-Furanoate + 5-C hloromethyl Furfural at 110°C ..................................... 17 Figure 3. Vapor Pressure Plot for 5-Chloromethyl Furfural and Ethyl 5-Methyl-2-Furanoate ............................. 18 Figure 4. Liquid Heat Capacities for 5-Chloromethyl Furfu ral and Ethyl 5-Methyl-2-Furanoate ......................... 19 Figure 5. Glass Still Used for Vapor Pressure and VLE Measuremen ts ................................................................ 20 Figure 6. Calorimeter used for Heat Capacity Measurements ................................................................ ............. 211 **Introduction**

Binary PTx measurements were performed on the 5-chlorometh yl furfural (CMF) and ethyl 5-methyl-2- furanoate (EMF) system at 80 and 110°C. Data were corr elated with the NRTL Activity Coefficient Model.

Vapor pressure measurements were performed on CMF and EMF. Results wer e correlated with the Antoine Equation.

Liquid heat capacity measurements were performed on CMF and E MF. Results were correlated using a linear fit of the form C = A + BT.

The CMF supplied by xF Technologies had a very short shelf-l ife. Multiple batches were used to complete the measurement program.2 **Results and Discussion**

**Vapor-Liquid Equilibrium**

The CMF + EMF system exhibited slightly positive deviation f rom ideality at both 80 and 110°C. The results of the PTx measurements are reported in Tables 1 and 2. These tabl es show the run number, the measured molar charge (z) compositions, the calculated molar liquid (x) and vapor (y) compositions, the measured and correlated total pressure (P), the calculated activity ( γ ) and fugacity ( φ ) coefficients, and the resulting relative volatility ( α ) for the system. NRTL parameters were used to correlate the m easured data and are shown at the bottom of each table. The temperature dependence of the NRTL τ ij parameters is shown in the following table (where all α ij

= 0.20):

**τ** ij **CMF EMF** 

**CMF** 0 T 164.77 1932 .1 +

**EMF** T

265.03 7765 .1 +

− 0

Figures 1 and 2 show plots of the total pressure versus composit ion for each of the isotherms studied. In these plots, open triangles represent the measured Px data, the long dashed line represents the correlation of the Px data, the short dashed line represents the correlated Py curve, and the solid line represents Raoult’s Law.

**Vapor Pressure**

Vapor pressure measurements have been completed for CMF and EMF. The measured saturation vapor pressure data are reported in Tables 3 and 4. The measured da ta have been correlated with the Antoine equation and compared with the correlation in the table. The parameters obtained from correlation of the Antoine equation are reported in the table. Figure 3 plots mea sured and correlated pressure for the two compounds.

**Heat Capacity**

Liquid heat capacity measurements were performed on CMF and EM F. The measured data have been correlated with an equation of the form C = A + B∙T and the correlation parameters A and B are reported in Table 5. Figure 4 plots the correlated heat capacities versus temperature.3 **Apparatus and Procedures**

**Vapor-Liquid Equilibrium**

The reported VLE data were measured using the glass still apparat us shown in Figure 5. The still had an internal volume of about 300 cc and was connected to a l arge ballast tank and to either an oil or mercury manometer. The line through the top of the still was used for c harging and degassing. Tap water was continually pumped through the condenser to maintain tem peratures to about 25°C.

A thermowell extended through the top of the still and into the liquid phase. Platinum resistance thermometers were used to measure the temperature in the still and in the bath. These thermometers were calibrated using ice and steam points and then referenced to a NIST traceable standard resistance thermometer. Temperatures were measured to an accuracy of ±0.02 5°C or better. The still was placed in a constant temperature bath that was controlled at a tempera ture 2.5°C warmer than the saturation temperature to promote refluxing. The liquid in the still was vigorously stirred to ensure good contact between the vapor and the liquid phases and to prevent superh eating in the liquid. The ballast tank pressure was used to control the still temperature. This pressure was adj usted to obtain the desired temperature. Dry nitrogen was used to adjust the system pressure.

A PTx run was initiated by evacuating the still and then cha rging it with a known amount of one of the compounds. The still was submerged in an isothermal bath an d the still contents were agitated with a magnetically coupled stirrer until equilibrium was established at the desired temperature. The still contents were then degassed by withdrawing the vapor into a weighed receiver. Dega ssing was done to remove any compounds from the still that were lighter than the compound s of interest. These light compounds can cause errors in the total pressure measurements. The vapor pressur e of the pure compound was then read. The still contents were again degassed and the pressure was again recorded. This pr ocedure was repeated until a stable vapor pressure was obtained.

Increments of the second compound were then added to the still . After each addition, the still contents were brought to equilibrium at the desired temperature and degassed. The pressure was then measured and recorded. This procedure was repeated until over half of the entire composition range had been traversed. The other half of the composition range was covered by repeat ing the same procedure starting with the second compound and adding increments of the first.

The system pressure was determined by reading each side of the oil man ometer, or mercury manometer above 40 mmHg total pressure, with a cathetometer to ±0.05 mm . The reference side of the manometer was connected to a McLeod gauge that was read to within ±0.01 mm. P ressures using the oil manometer were measured to within an estimated accuracy of ±0.02 mmHg. Pressu res greater than 40 mmHg were obtained using the mercury-filled manometer and are accurate to ±0.1 m mHg. Once equilibrium was established, the pressure and temperature were recorded. The ballast pressure was then i ncreased and the next addition of the second compound was made. After the still temperature had eq uilibrated, the still contents were degassed, and the ballast pressure was slowly adjusted until the sti ll temperature was approximately 2.5°C cooler than the bath temperature.

**Vapor Pressure**

The reported vapor pressure data were also measured using the glass sti ll apparatus shown in Figure 5 using the method described previously.4

**Heat Capacity**

Heat capacity measurements were made in the stirred calorimete r shown in Figure 6. The calorimeter was a 350 cc cell with an internal calibration heater and therm owell which contained a five junction thermocouple and a platinum resistance thermometer. The pressure was monit ored (but not recorded) by a precision pressure gauge teed to the calorimeter inlet line. The calorimeter was surrounded by an adiabatic shield which was heated independently by the surrounding bath fluid t o maintain the shield at the desired experimental temperature.

The calorimeter was charged with 250 to 350 grams of the l iquid to be tested, depending on the density of the compound. This ensured that the calorimeter was approximately 90% liquid-full by volume. The heat capacity measurements were made by electrically heating the calorimeter an d contents over a measured temperature interval with a known amount of electrical power. Heat-up r ates ranged from 0.50 to 1.25°C per minute, with each fluid being heated at four to five different rates. The r eported correlations are averaged over these runs. Data were continually logged every 4 seconds for the duration of the heating program.

The heat capacity of the contents was determined by subtracti ng the known heat capacity of the calorimeter. Water and o-xylene were used as calibration fluids to indep endently determine the heat capacity of the calorimeter. To do this, the calorimeter was heated electrically while filled with either pure water or pure oxylene. The heat capacity of the calorimeter was then determ ined by difference when the heat capacity of the water or o-xylene was subtracted from the total heat capa city over the temperature interval.

Table 6 lists the source and CAS numbers of the compounds u sed in this study.5 **Data Reduction**

**Vapor-Liquid Equilibrium**

The results of PTx measurements, which are total pressure as a funct ion of charge composition at constant temperature, were reduced to equilibrium phase compositions and activity and fugacity coefficients. The Soave equation of state [Soave, G., **Equilibrium Constants from a Modified Redlich-Kwong E quation of State**  , **Chem. Eng. Sci.** , 1972, 27, 1197-1203] was used to represent the vapor phase while the NRTL activity coefficient equation [Renon, H. and Prausnitz, J. M., **Local Compositions in Thermodynamic Excess Functions for Liquid Mixtures**  , **AIChE Journal** , 1968, 14, 135-144] was used to represent the liquid phase non -idealities in the data reduction procedure. The Soave binary interaction pa rameters used in the data reduction procedure were assumed to be zero.

To derive equilibrium phase compositions from PTx data, an iterative procedure is used to solve the basic equation of vapor-liquid equilibrium, given as follows: 

# ( )      

− = RT P

P V P x Py o i i o i o iii ii 

### exp

φ γ φ (1)

where P is the total pressure, y i is the vapor mole fraction of component i , φ i is the fugacity coefficient of component i , x

i is the liquid mole fraction of component i , γ i is the activity coefficient of component i , P i ° is the vapor pressure of component i at system temperature, φ i ° is the fugacity coefficient of component i at system temperature and corresponding vapor pressure of component i , and the exponential term is the Poynting correction where V i is the molar volume of component i . In the above expression, it is assumed that the molar volume of component i is equal to the partial molar volume of component i at these conditions. Pure component molar volumes were calculated from correlations of density data.

The data reduction procedure consists of fitting the pressure d ata to Equation (1) across the entire composition range by adjusting the parameters of the activity coefficient model. The NRTL activity coefficient equation was used in the data reduction procedure and is sho wn below:

NRTL equation:



## ( )                

+ +        

+ = 2 2 2 

### ln

AB A B AB AB

BA B A BA BA B A 

### G x x G G x x G x τ τ γ (2)



## ( ) 

              

+ +        

+ = 2 2 2 

### ln

BA B A BA BA

AB A B AB AB A B 

### G x x G G x x G x τ τ γ (3)

where ) exp( ) exp( BA BA AB AB G G ατ

ατ

−

= − = (4)6

As a beginning point, the ideal-solution parameters of the act ivity coefficient model are selected. Then, assuming the fugacity coefficients are unity, Equation (1) i s solved for the product Py i for each component. The calculated pressure is then the sum of these products: 

## ( ) 

# ∑ = i calc 

### Py P (5)

The vapor mole fraction for each component is then determin ed:

calc i i 

### P Py y = (6)

With values for the vapor-phase composition, the fugacity c oefficients can be calculated from the equation of state.

The next step is to correct the liquid composition for the amounts of each component in the vapor, return to the step in which the activity coefficients are calculated, a nd continue iterating until the calculated pressure converges.
This procedure is performed for each measured point across the composition range. The calculated pressures are compared with the measured pressures. The activity coefficien t parameters are adjusted to improve the fit of the total pressure data, and the entire procedure is r epeated until the best fit of the measured total pressure curve is obtained.

**Vapor Pressure**

Vapor pressure data have been correlated to the Antoine equatio n. The Antoine equation is as follows:



### C T B A P + + = ln (7)

The reported deviations have been calculated according to t he following equation:

corr meas 

### P P Dev log = (8)

The objective function used to correlate the vapor pressur e data was:

2 

### Dev OF = (9)

**Heat Capacity**

The heat capacities of the mixtures were determined by subtracti ng the known heat capacity of the calorimeter from the total heat capacity of the system. F or this experiment the calorimeter heat capacity was determined by first heating the calorimeter electrically while filled with pure water and pure o-xylene. The heat capacity of the calorimeter was determined by difference when the heat capacity of the water or o-xylene was subtracted from the total heat capacity over the tempera ture interval.7

The critical constants used in the data reduction procedu re are reported in Table 7. Critical constants for 5- chloromethyl furfural and ethyl 5-methyl-2-furanoate were calculated using a first order group contribution method. [Poling, B. E., Prausnitz, J. M., and O’Connell, J. P., **Method of Wilson and Jasperson** , **The Properties of Gases and Liquids**  , 2001, 2.9-2.12]8 **Acknowledgments**

We wish to express our gratitude to xF Technologies in Albuquerq ue for the opportunity to participate in their process design and research efforts. We greatly appreciate the gu idance and constructive support of Aviad Cahana and Luzheng Zhang xF Technologies.

The authors also wish to thank their coworkers who helped measur e the data with precision and meticulous effort; special thanks to Mark Swenson, Lane Gardner, and Gab riel Kelly.9 **Tables**

Table 1. PTx Measurement Results for Ethyl 5-Methyl-2-Fur anoate + 5-Chloromethyl Furfural at 80°C



### Relative Run Volatility # Charge Liquid Vapor Meas Calc CMF EMF CMF EMF EMF/CMF 2 100.00 100.00 100.00 1.49 1.49 1.000 1.492 1.000 1.000 4.89 1 2 94.97 94.97 80.59 1.78 1.76 1.002 1.389 1.000 1.000 4.547 2 90.13 90.13 68.15 1.99 1.99 1.006 1.311 1.000 1.000 4.269 2 85.22 85.23 58.86 2.18 2.19 1.014 1.246 1.000 1.000 4.032 2 80.31 80.31 51.57 2.38 2.38 1.023 1.195 1.000 1.000 3.830 2 75.42 75.42 45.60 2.54 2.55 1.033 1.153 1.000 1.000 3.659 2 70.50 70.50 40.49 2.72 2.71 1.044 1.119 1.000 1.000 3.513 2 65.32 65.32 35.77 2.87 2.88 1.057 1.090 1.000 1.000 3.382 2 60.41 60.41 31.78 3.03 3.04 1.070 1.069 1.000 1.000 3.276 2 55.55 55.55 28.18 3.19 3.19 1.082 1.052 1.000 1.000 3.186 1 53.33 53.33 26.62 3.26 3.25 1.088 1.045 1.000 1.000 3.150 1 48.40 48.40 23.36 3.42 3.40 1.100 1.033 1.000 1.000 3.077 2 45.63 45.63 21.63 3.48 3.49 1.107 1.027 1.000 1.000 3.041 1 43.44 43.44 20.30 3.55 3.55 1.113 1.023 1.000 1.000 3.015 1 38.57 38.57 17.48 3.70 3.70 1.124 1.016 1.000 1.000 2.964 1 33.92 33.92 14.94 3.85 3.84 1.134 1.011 1.000 1.000 2.922 1 29.31 29.31 12.55 3.98 3.98 1.143 1.007 1.000 1.000 2.888 1 24.60 24.60 10.25 4.13 4.13 1.152 1.004 1.000 1.000 2.858 1 20.02 20.02 8.11 4.27 4.27 1.159 1.002 1.000 0.999 2.835 1 15.34 15.34 6.05 4.40 4.42 1.166 1.001 1.000 0.999 2.815 1 10.65 10.65 4.08 4.55 4.56 1.171 1.000 0.999 0.999 2.800 1 6.03 6.03 2.25 4.73 4.71 1.176 1.000 0.999 0.999 2.789 1 0.00 0.00 0.00 4.90 4.90 1.179 1.000 0.999 0.999 2.780 Mole Percent CMF Pressure, mmHg Activity Coeff Fugacity Coeff

NRTL Equation Parameters: 

## τ 12 = - 1.6598 

## τ 21 = -1.0260 

## α = 0.2010

Table 2. PTx Measurement Results for Ethyl 5-Methyl-2-Fur anoate + 5-Chloromethyl Furfural at 110°C



### Relative Run Volatility # Charge Liquid Vapor Meas Calc CMF EMF CMF EMF EMF/CMF 2 100.00 100.00 100.00 8.85 8.85 1.000 1.317 0.999 0.999 3.32 2 2 95.00 95.01 85.80 9.73 9.82 1.001 1.250 0.999 0.999 3.148 2 90.09 90.10 75.18 10.58 10.66 1.005 1.197 0.999 0.999 3.004 2 85.18 85.19 66.62 11.34 11.44 1.010 1.154 0.999 0.999 2.882 2 80.23 80.23 59.37 12.12 12.16 1.016 1.119 0.999 0.999 2.778 2 75.49 75.49 53.36 12.91 12.82 1.023 1.093 0.999 0.999 2.693 2 70.47 70.48 47.71 13.61 13.49 1.031 1.070 0.999 0.999 2.616 2 65.61 65.61 42.77 14.26 14.12 1.039 1.052 0.999 0.999 2.554 2 60.73 60.74 38.22 14.88 14.74 1.047 1.039 0.999 0.999 2.501 2 55.82 55.83 33.98 15.45 15.36 1.055 1.028 0.999 0.999 2.456 2 45.40 45.40 25.86 16.57 16.66 1.071 1.012 0.999 0.998 2.384 1 35.20 35.20 18.85 17.80 17.92 1.083 1.004 0.998 0.998 2.339 1 30.24 30.25 15.73 18.42 18.54 1.088 1.002 0.998 0.998 2.324 1 25.80 25.81 13.07 18.97 19.09 1.091 1.001 0.998 0.998 2.314 1 20.76 20.77 10.20 19.65 19.73 1.094 1.000 0.998 0.998 2.307 1 15.78 15.78 7.53 20.28 20.36 1.095 1.000 0.998 0.998 2.303 1 10.76 10.76 4.98 20.88 20.99 1.096 1.000 0.998 0.998 2.302 1 6.07 6.07 2.73 21.55 21.59 1.095 1.000 0.998 0.998 2.303 1 0.00 0.00 0.00 22.36 22.36 1.092 1.000 0.998 0.998 2.309 Mole Percent CMF Pressure, mmHg Activity Coeff Fugacity Coeff

NRTL Equation Parameters: 

## τ 12 = - 1.6232 

## τ 21 = -1.0848 

## α = 0.2011 Table 3. Vapor Pressure Measurements for 5-Chloromethyl Fu rfural



### T o 

### C Measured Correlated % Deviation 72.04 0.78 0.81 -1.74% 77.04 1.16 1.17 -0.42% 80.00 1.49 1.44 1.43% 82.01 1.77 1.66 2.94% 87.09 2.35 2.32 0.64% 93.01 3.18 3.35 -2.35% 98.05 4.42 4.52 -0.99% 103.01 5.94 5.99 -0.31% 108.05 7.80 7.86 -0.31% 110.00 8.85 8.70 0.74% 113.00 10.12 10.15 -0.14% 118.02 13.04 13.00 0.10% 123.06 16.67 16.51 0.41%

Pressure, mmHg

lnP(mmHg) = 13.7867 – 2604.98 / (T (K) – 159.02) Calculated Normal Boiling Point = 250.03°C12 Table 4. Vapor Pressure Measurements for Ethyl 5-Methyl-2- Furanoate



### T o 

### C Measured Correlated % Deviation 54.92 0.67 0.75 -4.73% 56.96 0.85 0.88 -1.65% 60.06 1.16 1.12 1.36% 62.08 1.37 1.31 1.90% 65.00 1.62 1.63 -0.26% 65.01 1.73 1.63 2.76% 68.01 2.14 2.02 2.55% 70.00 2.43 2.32 2.00% 71.02 2.64 2.49 2.59% 75.03 3.43 3.26 2.20% 75.05 3.44 3.26 2.29% 80.00 4.90 4.48 3.87% 80.05 4.68 4.49 1.76% 85.02 6.25 6.08 1.18% 93.05 9.73 9.63 0.45% 105.02 17.52 18.00 -1.18% 110.00 22.36 22.92 -1.07% 115.01 27.69 28.92 -1.89% 125.02 42.47 44.73 -2.25% 135.02 58.13 66.87 -6.08% 145.00 92.21 96.90 -2.15% 155.03 132.42 137.01 -1.48% 155.02 131.95 136.95 -1.61% 165.07 184.78 189.10 -1.00% 175.03 254.85 254.88 -0.01% 185.06 347.73 337.47 1.30% 195.05 461.36 438.65 2.19% 205.01 620.01 560.68 4.37% 214.01 836.10 691.10 8.27%

Pressure, mmHg

lnP(mmHg) = 14.1537 – 2562.76 / (T (K) – 150.63) Calculated Normal Boiling Point = 218.26°C13 Table 5. Heat Capacity of 5-Chloromethyl Furfural an d Ethyl 5-Methyl-2-Furanoate

a. The measured temperature range for CMF is smaller due to solidification at low temperatures and decomposition at high temperatures. 

### CMF EMF A 1.2041 2.0007 B 0.002384 0.001346

Temp (°C) CMF EMF 10.0 a



### ----- a 

### 2.014 15.0 ----- 2.021 20.0 ----- 2.028 25.0 ----- 2.034 30.0 1.276 2.041 35.0 1.288 2.048 40.0 1.299 2.055 45.0 1.311 2.061 50.0 1.323 2.068 55.0 1.335 2.075 60.0 1.347 2.081 65.0 1.359 2.088 70.0 1.371 2.095 75.0 1.383 2.102 80.0 1.395 2.108 85.0 1.407 2.115 90.0 1.419 2.122 95.0 1.431 2.129 100.0 1.443 2.135 105.0 ----- 2.142 110.0 ----- 2.149 115.0 ----- 2.156 120.0 ----- 2.162

Correlations (J/g ∙° C) Heat Capacity (J/g ∙° C) = A + B ∙( T ° C)

Liquid Heat Capacity14 Table 6. Source and CAS Numbers of Chemicals



### Chemical Name Symbol CAS No. Supplier 5-Chloromethyl Furfural CMF 1623-88-7 xF Tech Ethyl 5-Methyl-2-Furanoate EMF 14003-12-4 xF Tech15 Table 7. Physical Properties of Chemicals



### Chemical Name Formula MW T c 

### , K P c 

### , bar Z c 

### ω 5-Chloromethyl Furfural C 6 

### H 5 

### ClO 2 

### 144.56 769.36 46.39 0.243 0.5349 Ethyl 5-Methyl-2-Furanoate C 8 

### H 10 

### O 3 

### 154.16 688.20 32.65 0.237 0.603616 **Figures**

Figure 1. PTx Plot for Ethyl 5-Methyl-2-Furanoate + 5- Chloromethyl Furfural at 80°C 0 1 2 3 4 5 6

0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00Pressure, mmHg

**Mole Fraction Ethyl 5-Methyl-2-Furanoate**

PTx Data Raoult's Law PTx Correlation PTy Correlation17 Figure 2. PTx Plot for Ethyl 5-Methyl-2-Furanoate + 5- Chloromethyl Furfural at 110°C 5 10 15 20 25

0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00Pressure, mmHg

**Mole Fraction Ethyl 5-Methyl-2-Furanoate**

PTx Data Raoult's Law PTx Correlation PTy Correlation18

Figure 3. Vapor Pressure Plot for 5-Chloromethyl Furfural and Ethyl 5-Methyl-2-Furanoate 0.10 1.00 10.00 100.00 1,000.00

2.00 2.20 2.40 2.60 2.80 3.00 3.20Pressure, mmHg

**1000/T (K)**

CMF Data CMF Correlation

EMF Data EMF Correlation19

Figure 4. Liquid Heat Capacities for 5-Chloromethyl Furfu ral and Ethyl 5-Methyl-2-Furanoate 1.00 1.10 1.20 1.30 1.40 1.50 1.60 1.70 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50

10 20 30 40 50 60 70 80 90 100 110 120Heat Capacity, J/g∙°C

**Temperature, °C**

CMF Correlation

EMF CorrelationFigure 5 . Glass Still Used for

20 Vapor Pressure and VLE MeasurementsFigure 6. Calorimeter used for Heat Capacity

21 Measurements