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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 gl ass 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.

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

the GC r etention 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 o 

### C which is reasonably close to what

exper imental data from distillation runs showed.

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### TABLE OF CONTENTS

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

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

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

Equipment

................................................................................................................................................. 4

RESULTS AND DISCUSSI ON ................................................................................................................... 6

Di stillation: ............................................................................................................................................... 6

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

SUMMARY AND CONCLUSI ONS ......................................................................................................... 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 in to the vial. (THF is used for dilution)

4. Mix t hem 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 Agile nt 19091J

- 113 Temp 325°C Data rate 20 Hz

HP

- 5 5% phenyl methyl siloxane H 2 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 Am bient

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 m in



### 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

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### RESULTS AND DISCUSSI ON

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) o 

### C. DVBDO cuts (6, 7, and 8)

were obtained at an overhead temperature range of (115-125) o 

### C. 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) o 

### C. DVBDO (97%) was obtained at a

temperature range of (115-120) o 

### C. 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

P bottom (mmHg) 10

P overhead (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 1 60.0 120.0

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

P bottom (mmHg) 10

P overhead (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 ( Gr een

et al

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

stru cturally 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.

Vi scosity 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 t o 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 o 

### C 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 ( o C & 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

Numbe r mmHg o C mmHg o C mmHg o C

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 0.34 5

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 o C

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 ( o C) P

(mmHg) Assuming  H Vap  S Vap

 Z (vap) (Cal/gmol) (Cal/gmol.C)

25.000 4.230 E

04 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 ( o C & 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 o C mmHg o C mmHg o C

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, Temperatur e: 0.300 o C

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 ( o C) P

(mmHg) Assuming  H Vap  S Vap

 Z (vap) (Cal/gmol) (Cal/gmol.C)

25.000 4.69E

03 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. V apor pressure of Ethylvinylbenzene Oxide ( EVB O)

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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

a nd their fit using Antoine equation

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### Table 12. Vapor Pressure for DVBMO

Antoine Coefficients ( o C & 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 o C mmHg o C mmHg o C

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 o C

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 ( o C) P

(mmHg) Assuming  H Vap  S Vap

 Z (vap) (Cal/gmol) (Cal/gmol.C)

25.000 2.93E

02 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 t emperature range of 50 to 180 o 

### C.

Figure 6. Vapor Pressure for DVBDO, DVBMO, EVBO



### SUMM ARY 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) o 

### C. DVBDO cuts (6, 7, and 8) were obtained at an overhead

temperature range of (115-125) o 

### C. 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) o 

### C. DVBDO (97%) was obtained at a temperature range of (115-120) o 

### C. 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.

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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 syst em

.

3. Turn on glycol cooling to overhead condenser (0 o 

### C).

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 0 

### C

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

20 o 

### C 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 0 

### C.

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 < 40 o 

### C 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 o 

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

Withi n 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 expe rimental 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

wil l 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.