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entral Report Index (CRI) Report

The Dow Chemical Company

Title

Distillation and Physical Properties Measurements for Divinylbenzene Dioxide, Divinylbenzene 

Monoxide, and Ethylvinylbenzene Oxide

Author(s) and Userid(s)

Alkhawaldeh, Ammar* (U398645); Fowler, Tammy (U241382); Jean, Dave (U649356); Pham, Khiet 

(U145023); Solis, Juan (U224480) ; Srivastava, Rakesh* (U081611)

Reviewer(s)and Userid(s)

Young, Thomas (TC) (U074037)

Patent Status Date Issued Page Count Lab Report Code

N/A 06/18/2010 21

Geographic Location Department Databook Number(s) CRI Number

Freeport, TX Epoxy Process 

Research 2010002363

Abstract 

This report describes the determination of various physical properties of Divinylbenzene Dioxide 

(DVBDO), Ethylvinylbenzene Oxide (EVBO), and Divinylbenzene Monoxide (DVBMO). 

The high purity DVBDO and EVBO samples were obtained via distillation using a 10-tray Oldershaw 

column connected to a magnetic reflux head. The vapor pressure of DVBDO and EVBO were measured 

in a glass still which consists of a 250 mL filter flask attached to a condenser. The measured vapor 

pressure data were correlated using the Antoine equation in the Thermal ANTOINE program with 

Thomson‟s constraint. 

Highly pure samples of DVBMO could not be obtained via distillation, so, an alternative method using 

the GC retention time was used for obtaining vapor pressure. Retention time data for EVBO, DVBMO, 

and methane were recorded while the GC oven was maintained isothermally. 

Measurements showed that vapor pressure values of DVBMO and EVBO are very close which is 

consistent with the experimental observations from the distillation process. Moreover, at 2 mmHg, the 

overhead temperature at which DVBDO come out is ~ 122 oC which is reasonably close to what 

experimental data from distillation runs showed. 
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TABLE OF CONTENTS

EXPERIMENTAL ........................................................................................................................................ 3

Material ..................................................................................................................................................... 3

Analytical .................................................................................................................................................. 3

Equipment ................................................................................................................................................. 4

RESULTS AND DISCUSSION ................................................................................................................... 6

Distillation: ............................................................................................................................................... 6

Physical Properties .................................................................................................................................... 7

SUMMARY AND CONCLUSIONS ......................................................................................................... 20
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EXPERIMENTAL 

Material 

The DVBDO crude used in this study was produced in the Freeport Epoxy R&D 

Analytical 

Gas Chromatograph (GC): 

An Agilent-6890 Series Gas Chromatograph equipped with a flame ionization detector, auto injector, and 

ChemStation software was used. The column used was an HP-5 , (30 m long by 0.32 mm I.D. by 0.25 

micron film thickness packed with 5% Phenyl Methyl Siloxane). Distilled product was analyzed by an 

internal standard weight percent method after dilution of the sample in Tetrahydrofuran (THF). Samples 

of known composition of DVBDO, DVB, EVBO, and DVBMO were used to calibrate the method.

Sample preparation for GC analyses (An internal standard was used in preparing the GC method): 

1. Add 0.2 g DVBDO sample into 5 dram vial 

2. Add 0.04 g Diglyme into the same vial (Diglyme is used as the internal standard) 

3. Add 0.4 g THF into the vial. (THF is used for dilution) 

4. Mix them well before transferring it to GC vial 

The GC method used is shown in Table 1. 

Table 1. GC Method 

OVEN INLET

Initial temp. 60 °C Max. temp 330 °C Mode Split

Initial time 1.00 min Equil. Time 2.00 min Initial temp 280 °C

Ramps Pressure 8.00 psi

# Rate Final temp Final time Split ratio 50:1

1 5.00 150 °C 0.00 Split flow 76 mL/min

2 10.00 250 °C 18.00 Total flow 80.7 mL/min

3 0.0 (off) Gas saver 2.00 min

4 Post temp 60 °C Saver flow 20.0 mL/min

Post time 0.00 min Saver time 2.00 min

Run time 47.00 min Gas type Helium

COLUMN DETECTOR (FID) SIGNAL

Model Agilent 19091J-113 Temp 325°C Data rate 20 Hz

HP-5 5% phenyl methyl siloxane H2 flow 30.0 mL/min Type Front

Max temp 325 °C Air flow 300.0 mL/min Save data On

Length 30.0 m Mode Constant column

+ makeup flow

Zero 0.0 (off)

Diameter 320.00 μm Combined flow 40.0 mL/min Range 0

Thickness 0.5 μm Makeup flow off Fast peaks Off

Mode Constant pressure Makeup gas Helium Attenuation 0
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Pressure 8.00 psi Flame On

Initial flow 1.5 mL/min Electrometer On

Average velocity 27 cm/sec Lit offset 2.0

Outlet pressure Ambient

INJECTOR 

Sample washes 3

Sample pumps 3

Injection volume 1.0 μL

Syringe size 10.0 μL

Postinj solvent A washes 4

Postinj solvent B washes 4

Viscosity delay 2 sec

Plunger speed Fast

Preinjection dwell 0.00 min

Postinjection dwell 0.00 min

Equipment 

DVBDO crude was distilled using the experimental distillation set up shown in Figure 1. A 10-tray 

Oldershaw column connected to a magnetic reflux head, condenser, and a cold trap was used. The system 

is equipped with three different vacuum pumps and the boiler pot is heated with a heating mantle. 

Pressure and temperature were controlled. The experimental procedure is shown in Appendix A. 
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Figure 1. Lab Scale DVBDO Distillation Apparatus

T P

Magnetic Reflux

Head

V1

V2

V3

V4

T

P

Cold Trap

VP-1

VP-2

VP-3

Lab Scale Distillation of DVBDO

T P

Magnetic Reflux

Head

V1

V2

V3

V4

T

P

Cold Trap

VP-1

VP-2

VP-3

Lab Scale Distillation of DVBDO
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RESULTS AND DISCUSSION

Distillation: 

DVBDO crude (78% DVBDO) was distilled to obtain higher purity (99%) DVBDO and EVBO. 

Distillation was run at 2 mmHg and a reflux ratio of 3. The composition of the DVBDO crude is show in 

Table 2

For the 99% purity DVBDO, the results are shown in Table 3. The light cuts (Cuts 1, 2, 3, 4) which are 

mainly EVBO, were obtained at an overhead temperature range of (66-74) oC. DVBDO cuts (6, 7, and 8) 

were obtained at an overhead temperature range of (115-125) oC. About 72% of the crude was recovered 

as a product of which 72% is DVBDO (~99% purity) and 23% is EVBO (90-95% purity) 
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Table 4 shows the distillation results for the 99% EVBO from crude DVBDO. Cuts 3-8 which are mainly 

EVBO, were obtained at an overhead temperature range of (66-71) oC. DVBDO (97%) was obtained at a 

temperature range of (115-120) oC. The percentage recovery of products is about 74% of which ~ 19% is 

EVBO (99% purity) and ~ 81% DVBDO (97% purity) 

Table 2. DVBDO Crude Composition 

Component wt%

EVBMO 18.8

DVBMO 1.7

DVBDO 78.2

Uncalib. 1.3

Table 3. Distillation cuts for DVBDO (99% purity) and EVBO (< 95% purity) 

Reflux Ratio 3

Pbottom (mmHg) 10

Poverhead (mmHg) 2

wt (g)

EVBO

wt%

DVBMO

wt%

DVBDO

wt% Temperature (C)

Crude 1563.5 18.8 1.7 78.2 Bottom Overhead

Cut1 98.5 90.3 1.6 0.1 120.0 66.0

Cut2 77.7 93.3 3.0 0.6 125.0 69.0

Cut3 40.6 95.2 1.8 0.0 130.0 70.0

Cut4 45.1 88.3 4.7 0.1 140.0 74.0

Cut5 29.1 37.4 10.6 46.9 150.0 109.0

Cut6 57.9 0.7 0.4 98.4 155.0 115.0

Cut7 394.5 0.0 0.1 99.4 160.0 120.0

Cut8 413.2 0.0 0.0 99.1 160.0 125.0
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Table 4. Distillation of EVBO 

Reflux Ratio 3

Pbottom (mmHg) 10

Poverhead (mmHg) 2

wt (g)

EVBO

wt%

DVBMO

wt%

DVBDO

wt% Temperature (C)

Crude 884.4 18.2 1.6 78.4 Bottom Overhead

Cut1 13.5 82.9 0.3 0.2 114.0 63.0

Cut2 19.1 97.9 0.3 0.5 116.0 65.0

Cut3 32.8 99.3 0.4 0.0 117.0 66.0

Cut4 6.4 99.1 0.4 0.2 119.0 68.0

Cut5 33.8 99.2 0.8 0.0 119.0 69.0

Cut6 4.4 99.2 0.1 0.0 121.0 70.0

Cut7 5.6 99.1 1.2 0.0 120.0 70.0

Cut8 8.0 99.0 3.2 0.0 121.0 71.0

Cut9 520.0 0.6 0.3 97.5 145.0 115.0

Cut10 12.2 0.6 0.3 97.5 154.0 120.0

Physical Properties 

Vapor pressure and density data of the three components in this study were measured. 

Vapor Pressure Measurement Method 

The vapor pressure and boiling point of DVBDO and EVBO were measured in a glass still which consists 

of a 250mL filter flask attached to a condenser as described in ASTM standard E 1719-97. The 

temperature of the liquid in the flask was measured with an accuracy of ±0.05°C by a calibrated platinum 

resistance thermometer inserted into the liquid. The temperature was logged by a computerized data 

acquisition system. The still was charged through top of the flask. After charging, the still was evacuated 

and refilled with dry nitrogen to remove moisture and oxygen. The base of the still was then immersed in 

a silicone oil bath and the oil bath was heated. The details of the measurement technique and data 

analysis to get Antoine equation coefficients for vapor pressure and boiling point can be found in the a 

CRI by Fowler et al., 2007. 

Since highly pure samples of DVBMO could not be obtained via distillation, an alternate method using 

the GC retention time was used for obtaining vapor pressure as described in a previous CRI report (Green 

et al., 1992). Meta or Para EVBO was used as a reference compound for the method since they are 

structurally similar to DVBMO and their vapor pressure was measured independently in this study. 

Retention time data for EVBO, DVBMO, and methane were recorded while the GC oven was maintained 

isothermally. A syringe was used to pull the DVBDO sample, and then using the same syringe, a sample 

of the methane gas was added. The liquid/gas sample was then shot in the GC. The GC retention data are 

shown in 
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Table 5. The GC conditions for this method are similar to the ones presented in Table 1 except for the 

column. A DB-5 column was used and the analyses were run isothermally.
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Table 5. GC Retention Times for DVBMO Sample 

GC Oven

Temperatu

re

(C) 70 80 90 100 110

Componen

t

Retentio

n %

Retentio

n %

Retentio

n %

Retentio

n %

Retentio

n %

Time Time Time Time Time

Methane 1.61 0.03 1.58 0.03 1.56 0.03 1.53 0.03 1.50 0.03

Chloroform 2.72

13.2

5 2.42

12.9

6 2.20

13.2

2 2.03

13.0

6 1.91

13.1

2

Impurities 3.02 0.02 2.65 0.02 2.38 0.02 2.18 0.01 2.02 0.02

m-EVB 40.54 0.60 26.31 0.60 17.78 0.60 12.45 0.60 9.08 0.60

p-EVB 52.64 0.59 27.65 0.58 18.65 0.59 13.02 0.58 9.47 0.59

m-DVB 49.03 4.47 31.41 4.43 20.96 4.48 14.48 4.46 10.42 4.46

p-DVB 52.57 1.59 33.58 1.58 22.33 1.61 15.37 1.60 11.02 1.60

Unknown N/A N/A N/A N/A 25.59 0.04 17.59 0.05 12.57 0.06

Unknown N/A N/A N/A N/A 28.42 0.06 19.25 0.05 13.58 0.09

m-EVBMO 128.42 7.92 77.78 7.94 49.51 7.92 32.14 7.90 14.75 0.05

p-EVBMO 137.85 6.84 82.91 6.86 52.49 6.89 34.00 6.84 21.71 7.85

m-DVBMO 158.30

34.6

0 94.30

34.6

4 58.51

34.7

4 37.55

34.5

6 22.93 6.73

p-DVBMO 169.58

16.6

8 100.76

16.8

0 62.37

16.7

3 40.03

16.6

2 25.14

34.3

1

m-DVBDO 507.49 8.71 283.03 8.80 164.94 8.46 71.45 0.19 27.13

16.4

7

p-DVBDO 537.56 4.71 299.58 4.76 174.46 4.63 99.83 8.80 41.78 0.09
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Density Measurement Method:

The density was measured using an Anton Paar density meter, model DMA 5000 (accuracy ~ 1%) (serial 

#241328). The temperature of the cell is regulated internally and measured by two integrated Pt 100 

platinum thermometers. Before the measurement of the sample the equipment was calibrated by 

performing adjustment on both water and air as described in the manual for the DMA 5000 and TECHSOP-014. The validity of the Anton Paar DMA 5000 density meter is checked by testing the density of 

the air and nanopure water and compared to the density tables in back of the Anton Paar DMA 5000 

Density Meter Instruction Handbook. In addition, toluene was also run as a standard to ensure the 

accuracy of the temperature of the DMA 5000. The Pt 100 thermometers, which read the temperature of 

the sample cell, are inaccessible to the operator of the instrument. The toluene runs provide an indirect 

test of accuracy of temperature measurement. All testing is done in replicate of three with the average of 

the three results being calculated. 

Viscosity Measurement Method: 

The viscosity data were measured using a Brookfield digital dynamic viscometer model DV-II with the 

Thermosel adapter/spindle #18 (accuracy ~ 1%). The adapter has a built-in heater assembly which was 

used to regulate the temperature. Five data points were collected at each temperature and the reported 

values are the numerical average of these points. 

Vapor Pressure and density results: 

DVBDO and EVBO 

The measured vapor pressure data were correlated using the Antoine equation in the Thermal ANTOINE 

program with Thomson‟s constraint. The details of Antoine fitting program are shown in Appendix B. 

The first two data points at 1 mmHg and 2 mmHg were omitted since they did not have a good fit and the 

data at low pressures are usually expected to be not as good as that at higher pressures. There were 

enough data points acquired at the higher temperatures to compensate for omitting these two points. The 

experimental data and correlation are shown in Table 6 and Table 7 . The plots of the data along with the 

Antoine equation correlations for the two compounds are shown in Figure 3 and Figure 4 . At 2 mmHg, 

the overhead temperature at which DVBDO comes out is ~ 122 oC which is reasonably close to what 

experimental data from distillation runs showed (Table 3 and 
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Table 4) 

Table 9 show the density measurements for DVBDO and EVBO. The viscosity measurements for EVBO 

are presented in Table 10

Table 6. Vapor Pressure Data for DVBDO 

Antoine Coefficients (oC & mmHg)

A B C

8.4092 2527.66 189.048

Vapor Pressure of DVBDO

Point P Exp. T Exp. P Calc T Calc P Diff T Diff

Number mmHg oC mmHg oC mmHg oC

1+ 1 121 1.825 111.313 -0.825 9.687

2+ 2 127.3 2.647 122.527 -0.647 4.773

3 5 139.4 5.191 138.703 -0.191 0.697

4 10 151.6 9.753 152.103 0.247 -0.503

5 15 159.9 14.606 160.461 0.397 -0.561

6 20 166.3 19.687 166.645 0.313 0.345

7 25 171.5 24.896 171.594 0.104 -0.094

8 40 183.3 41.39 182.483 -1.39 0.817

Standard Deviation, Temperature: 0.608 oC

Standard Deviation, Pressure: 0.671 mmHg

Standard Error in Log (P): 1.186 E-02

Thomson's Rule C Value: 188.859 

Calculated Vaporization Data:

T (oC)

P 

(mmHg) Assuming H Vap S Vap

Z (vap) (Cal/gmol) (Cal/gmol.C)

25.000

4.230 E04 1.00 22315 46.23

269.164 760.000 0.96 15452 28.49
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Table 7. Vapor Pressure Data for EVBO 

Antoine Coefficients (oC & mmHg)

A B C

5.72578 934.649 91.034

Vapor Pressure of DVBDO

Point P Exp. T Exp. P Calc T Calc P Diff T Diff

Number mmHg oC mmHg oC mmHg oC

1 5 95.1 5.063 94.898 -0.063 0.202

2 10 106.4 9.813 106.742 0.187 -0.342

3 25 124.82 24.876 124.927 0.124 -0.107

4 50 141.32 50.497 141.072 -0.497 0.248

5 100 160.15 101.115 159.825 -1.115 0.325

6 200 181.54 198.068 181.875 1.932 -0.335

Standard Deviation, Temperature: 0.300 oC

Standard Deviation, Pressure: 1.02 mmHg

Standard Error in Log (P): 17.321 E-03

Thomson's Rule C Value: 194.876 

Calculated Vaporization Data:

T (oC)

P 

(mmHg) Assuming H Vap S Vap

Z (vap) (Cal/gmol) (Cal/gmol.C)

25.000

4.69E03 1.00 28236 70.86

237.492 760.000 0.96 9919 19.42
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Figure 3. Vapor pressure of Divinylbenzene Dioxide 

Figure 4. Vapor pressure of Ethylvinylbenzene Oxide (EVBO)
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Table 8. Density Measurements for DVBDO 

Table 9. Density Measurements for EVBO 

Temperature Density Standard 

C g/cm3 Deviation

20 1.005974 1.61E-05

25 1.002143 6.66E-06

50 0.981969 3.21E-06

80 0.956867 7.09E-06

Table 10. Viscosity of EVBO

Temperature Viscosity Standard 

C CP Deviation

25 2.06 <10-6

50 1.39 <10-6

75 0.44* 1.26E-02

100 0.73* 2.06E-02

* Results are below the 1 cP accuracy limit of the instrument. 

Temperature Density Standard 

°C g/cm3 Deviation

0 1.17300 7.8102E-06

5 1.16888 6.5064E-06

10 1.16474 3.7859E-06

15 1.16061 4.9329E-06

20 1.15645 1.5275E-06

25 1.15233 1.1547E-06

30 1.14819 4.7258E-06

35 1.14401 2.5166E-06

40 1.13986 1.7321E-06

45 1.13562 1.3051E-05

50 1.13153 4.0415E-06

55 1.12737 8.1854E-06

60 1.12318 6.0277E-06

65 1.11901 3.0551E-06

70 1.11367 3.6937E-05

75 1.11037 3.6918E-05

80 1.10521 4.9339E-05
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DVBMO 

DVBMO polymerizes at high temperatures, hence, highly pure samples (99%) could not be obtained via 

distillation to use for vapor pressure measurements. An alternative method (described above) was used to 

estimate the vapor pressure for DVBMO. 

Table 11 shows the vapor pressure of DVBMO calculated using the GC retention analysis as described 

earlier in this report. Retention data for m and p EVBO were used as reference and an average value was 

calculated for DVBMO based on these two references as shown in the table below. For comparison 

purposes vapor pressure of EVBO is also shown in the Table 11 Figure 5 shows the calculated values of 

DVBMO vapor pressure from GC method. The data obtained using the GC method was used to correlate 

the Antoine equation constants as shown in Table 12. 

Table 11. Vapor Pressure of DVBMO calculated using the GC retention time analysis 

T (°C)

P (mmHg) P (mmHg) P (mmHg) P (mmHg)

m-DVBMO p-DVBMO

Average VP 

(DVBMO) VP (EVBO)

70 1.03 1.03 1.03 1.32

80 1.95 1.95 1.95 2.45

90 3.52 3.51 3.52 4.36

100 6.13 6.09 6.11 7.45

110 10.26 9.98 10.12 12.30

m-EVBMO 

retention time 

as reference

p-EVBMO 

retention time 

as reference

EVBO VP for 

comparison

Figure 5. Calculated values of DVBMO vapor pressure from GC method

and their fit using Antoine equation 
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Table 12. Vapor Pressure for DVBMO 

Antoine Coefficients (oC & mmHg)

A B C

7.6139 2022.14 196.081

Vapor Pressure of DVBDO

Point P Exp. T Exp. P Calc T Calc P Diff T Diff

Number mmHg oC mmHg oC mmHg oC

1 1.03 70 1.033 69.953 -0.003 0.047

2 1.95 80 1.947 80.022 0.003 -0.022

3 3.52 90 3.511 90.043 0.009 -0.043

4 6.11 100 6.084 100.08 0.026 -0.08

5 10.12 110 10.17 109.9 -0.05 0.1

Standard Deviation, Temperature: 7.227E-02 oC

Standard Deviation, Pressure: 2.848E-02 mmHg

Standard Error in Log (P): 1.941 E-03

Thomson's Rule C Value: 196.081 

Calculated Vaporization Data:

T (oC)

P 

(mmHg) Assuming H Vap S Vap

Z (vap) (Cal/gmol) (Cal/gmol.C)

25.000

2.93E02 1.00 16828 36.25

231.154 760.000 0.96 12376 24.54
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Figure 6 shows a comparison of the calculated vapor pressure values for DVBDO, EVBO, and DVBMO 

at a temperature range of 50 to 180 oC.

Figure 6. Vapor Pressure for DVBDO, DVBMO, EVBO 

SUMMARY AND CONCLUSIONS 

DVBDO crude (78% DVBDO) was distilled to obtain higher purity (99%) DVBDO and EVBO. The 

Distillation was run at 2 mmHg and a reflux ratio of 3. 

For the 99% purity DVBDO, the light cuts (Cuts 1, 2, 3, 4) which are mainly EVBO, were obtained at an 

overhead temperature range of (66-74) oC. DVBDO cuts (6, 7, and 8) were obtained at an overhead 

temperature range of (115-125) oC. About 74% of the crude was recovered as a product of which 55% is 

DVBDO (~99% purity) and 17% is EVBO (< 95% purity) 

For the 99% EVBO, cuts 3-8 which are mainly EVBO, were obtained at an overhead temperature range 

of (66-71) oC. DVBDO (97%) was obtained at a temperature range of (115-120) oC. the percentage 

recovery of products is about 74% of which ~ 10% is EVBO (99% purity) and ~ 60% DVBDO (97% 

purity) 

Vapor pressure data for DVBDO, EVBO, and DVBMO were obtained. Density measurements were also 

obtained for DVBDO and EVBO. Moreover, viscosity was measured. 

0

50

100

150

200

250

40 60 80 100 120 140 160 180 200

Temperature (C)

Vapor Pressure (mmHg)

EVBO

DVBMO

DVBDO
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REFERENCES 

Dow References are not approved for external release. 

ASTM standard E 1719-97, Standard Test Method for Vapor Pressure of Liquids by Ebulliometry, March 

10, 1997
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Appendix A 

Experimental Procedure for Distillation Apparatus

1. Add dry ice to the Dewar holding the cold trap. 

2. Turn on the power to the system.

3. Turn on glycol cooling to overhead condenser (0oC). 

4. Check for vacuum leaks prior to adding any chemicals to system. Opens valves V1, V2, and V4. 

Turn on the vacuum pumps VP-1 and VP-2. System top pressure should be less than 12 mmHg. If 

pressure is > 12 mmHg, check for leaks in tubing connections and ground glass joints. Secure tubing 

and re-grease as needed then repeat the vacuum test until a system top pressure of < 8 mmHg is 

obtained. 

5. After ensuring vacuum is sufficient, turn off vacuum pumps 1 and 2. Then release vacuum using 

valve V3. 

6. Add desired amount of crude product solution to be distilled (Maximum volume of crude to add 

should be 70% of the bottom flask volume) 

7. Startup of Vacuum System. 

a. Make sure that the glycol bath temperature is < 5 0C 

b. Turn on magnetic stirring. 

c. Open valves V1, V2, and V4 

d. Make sure the magnet is turned off so the distillation head is set for total reflux. 

e. Turn on vacuum pumps VP-1 and VP-2. 

f. Slowly close valve V3 to increase vacuum in the system to around 5 mm Hg. Watch for 

excessive boil up. If vigorous bubbling is observed, open valve 3 slowly. 

g. If top pressure reaches the desired value of (i.e. 2-10 mm Hg), proceed with the next step. 

Otherwise, investigate possible sources of leaks until desired pressure is obtained. 

8. Start Heating in the Bottoms Pot - Turn on temperature controller. Gradually increase the set point in 

20oC increments until the desired operating temperature is reached. Monitor the distillation rate as the 

system heats up. Adjust the temperature set point as needed to achieve the desired boil up rate. The 

heating mantle will be switched off if its temperature reaches 201 0C. 

9. Once the system is at equilibrium as indicated by a steady drop rate from the condenser (or set of 

parameters desired), adjust the reflux rate by turning on the reflux magnet to obtain the desired 

collection rate. 

10. Periodically record the distillation conditions, e.g. system pressures, bottoms temperature, and 

overheads vapor temperature. 

11. Sampling overheads: (refer to Figure 1) 

a. Close valves V2 and V4. 

b. Adjust valve V3 to bleed off vacuum in receiver flask without upsetting pressure in main 

distillation pot and distillation head. 
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c. Carefully remove receiver flask. Pour contents into appropriate container. This sample will be 

analyzed by GC. 

d. Install a clean receiver flask. Re-grease the ground glass joint when installing flask. 

e. Connect a vacuum pump VP-3 to valve V3 and receiver flask. Turn on vacuum pump VP-3 until 

vacuum in receiver flask matches that of the main distillation head. 

f. Close valve V3 and open valves V2 and V4. Turn off vacuum pump VP-3 (VP-3 is only used 

during sampling of receiver flask) 

g. Collection of overheads will always take place as long as the reflux magnet is on. After valve V4 

is open, the collection of the overheads will be allowed to collect in the receiver flask. 

12. Shutdown: 

a. Lower pot temperature controller set point to 20°C. Physically unplug the heating mantle power 

cord before leaving for the day. 

b. When pot temperature drops to < 40oC in bottoms liquid, then shut off vacuum pumps VP-1 and 

VP-2. 

c. Let vacuum bleed off slowly through valve V3. If vacuum needs to be bled off faster, and then 

slowly open the needle valve located to the right on the wall of the hood. 

d. Turn off glycol bath to overhead condenser. 

After the liquid in bottoms flask cools to < 40 oC, then it is safe to handle. Disassemble the glassware 

carefully 

13. Retain a sample of the bottoms liquid for analysis. 

14. Clean glassware with acetone or other appropriate solvents and allow to air dry 

15. Dispose of waste in lab packs according to department procedure. 
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Appendix B 

ANTOINE program

“The ANTOINE program fits vapor pressure data to the Antoine equation of the form logP = A - B/(T + 

C). Data can be in mmHg, atm, psia, kPa for pressure and C, K, F or R for temperature. 

 

Within ANTOINE you can do constrained or unconstrained fitting, look at plots of the vapor pressure 

data, or delete points from fitting. Since constraints are available the minimum number of vapor pressure 

points required are 3 for unconstrained fits, 2 for fits with one constraint and 1 for fits with two 

constraints. 

Various constraints (Thomson or Trouton) can be optionally applied during the fitting procedure. The 

Thomson constraint constrains the C constant to provide an approximately correct curvature. The 

Trouton constraint forces an approximately correct heat of vaporization at the normal boiling point. 

Trouton's "constant" is the entropy of vaporization at the normal boiling point. This is normally 20-23 

cal/(mol K) for non-hydrogen-bonded fluids and 23-26 cal/(mol K) for hydrogen-bonded fluids. A better 

idea of Trouton's constant for a particular molecule can come from looking at a homologous series or 

molecules of similar structure. Advice to the user is as follows: 

1. Try the unconstrained fit first. If the Trouton constant and the C value are close to the expected values 

this is probably the best fit. Close can be defined as Trouton constant within +- 1-2 of expected 

value and C constant within +-20 of Thomson's rule value. Warnings are issued by ANTOINE when 

large deviations exist for either. 

2. If the Trouton constant and/or C value deviate noticeably from the expected values a more meaningful 

fit may result from constrained fitting. But you may want to look at the plot first to see if any of 

the experimental points are noticeably inconsistent. If so, delete those points and re-fit without 

constraints. 

3. Recommended procedure is to then try the Thomson constraint first to force an approximately correct 

curvature. If this does not result in an improved Trouton constant then you may need to try either the 

Trouton constraint or the combined Thomson/Trouton constraints. 

4. Final decision on which fit is the "best" comes with experience. Normally data of very high quality 

will require no constraints and the use of constraints becomes more and more essential, and apparent, as 

the quality of the data decreases (usually denoted by increased scatter in the data). Neither the Thomson 

or Trouton constraint is appropriate for fluids which display specific vapor-phase association (small 

carboxylic acids or HF). 

WARNING: If the input data file is created or modified using a word processor, be sure to use COURIER 

font and save the file as a simple ASCII text file with carriage return and line feed characters at the end of 

each line.