HEATS OF COMBUSTION OF SOME NITROALCOHOLS

Citation preview

HEATS OF COMBUSTION OF SOME NITROALCOHOLS A Thesis Submitted to the Faculty of Purdue University by Robert Marion Currie In Partial Fulfillment of the Requirements for the Degree of Doctor of philosophy August, 1950

P U R D U E U N IV E R S IT Y

T H IS IS T O C E R T IF Y T H A T T H E T H E S I S P R E P A R E D U N D E R MY S U P E R V I S I O N

5 1 ______ Robert Marion Currie

E N T IT L E D

H e a ta

o f

C o m b u s tio n

c f

Som e

’l i t r o a l c c h o l a

C O M P L IE S W IT H T H E U N IV E R S IT Y R E G U L A T IO N S O N G R A D U A T IO N T H E S E S

A N D I S A P P R O V E D B Y M E A S F U L F IL L IN G T H IS P A R T O F T H E R E Q U IR E M E N T S

FOR TH E D EG R EE O F

Doctor of Philosophy

BOR IN C H A B O K O F T H W H

H

kad o f

S

chool or

T O T H E L IB R A R IA N i----T H IS T H E S I S I S N O T T O B E R E G A R D E D A S C O N F ID E N T IA L .

P

k ta tm k st

ACKNOWLEDGE®! TS The author wishes to express his appreciation to Dr. D. E. Holcomb, director of the research, to his successor, Dr. C. 0. Bennett, and to various others for their help in the solution of problems arising from the research.

TABLE OF CONTENTS

a b s t r a c t ............................................................

i

IN IROJUCTION........................................................

1

REVIEW OF THE LITERATURE............................................

2

Calorimetric Methods............................................. Availability of the Nitroalcohol3................................ Physical Properties..................................

2 3

METHOD OF INVESTIGATION.............................................

6

APPARATUS...........................................................

B

The Bomb......................................................... 3 The Calorimeter Can.............................................. 8 The Jacket....................................................... 8 Provisions for Agitation of the Vater............................ 13 The Differential Thermopile..................................... 13 Temperature Measurements........................................ 14 The Firing Assembly...................................... 14 Balances.................................. Gas Analysis Apparatus.......................................... 15 SOURCE AND PURIFICATION OF SAMPLES..................................

19

3-nitro-2-butanol.............................................. 2-nitro-2-methyl-l,3-propanediol................................ 2-nitro-2-methyl-l-propanol.................................... 2-nitro-2-ethyl-l,3-propanediol................................. 2-nitro-2-methyl-3-pheny1-1-propanol............................. 2-nitro-2-methy1-1-phenyl-1-propanol............................. 2-nitro-2-pr opyl-1,3-propanediol................................ 2-ni tro-2-isopr opyl-1,3-propanediol.............................. Tris(hydroxymethyl)nitromethane................................. TTinitromethane................................................ Hydrazine Hydrate...............................................

20 20 20 20 21 21 21 21 21 22 22

EXPERIMENTAL PROCEDURE.............................................

23

Calibration of the Calorimeter...................................

23

Preparation for the Experiment............................... The Equilibrium Period...................................... The Initial Rating period.................................... The Experimental Period....................................... The Final Rating Period....................................... Concluding the Experiment....................................

24 26 26 27 27 27

TABLE OF CONTACTS ( C o n t ’ d . )

Page Heats of Combustion of Experimental Samples..................

28

CALCULATIONS....................................................

29

Correction of Calorimetric Data.

...........................

29

Thermometer Corrections................................... height Corrections........................................ Heat Evolved by Combustion of Fuse Vire................ Heat Evolved by Electrical Energy...................... Heat Evolved by Formation of Nitric Acid.............. Correction for Heat from External Sources.................

29 29 29 30 30 30

The Heat Capacity of the Calorimetric System.................

32

Heats of Combustion

33

The Heat The Heat The Heat

of Combustion of Combustion of Combustion

........... UnderBomb Conditions............ Under Standard Conditions ... at Constant Pressure.............

33 33 36

of Formation.................................

36

Units, Constants and Uncertainties...........................

39

EXPERIMENTAL RESULTS............................................

40

DISCUSSION OF RESULTS...........................................

58

Standard Heats

Calibration Experiments..................................... Heat of Combustion Experiments............................... Accuracy of the Data........................................ Precision of the Data............ Correlation of Heat of Combustion with Oxygen Balance....... *

58 58 59 60 61

CONCLUSIONS.....................................................

66

APPENDIX A:

DEFINITION OF TiRMS................................

67

APPENDIX B:

DERIVATION OF EQUATIONS FOR HEAT EVOLVED OUTSIDE OF THE CALCRIMETRIC BOMB........................

69

SAMPLE CALCULATIONS................................

72

BIBLIOGRAPHY....................................................

83

VITA

85

APPeNDIX C:

LIST OF TABLES AXD FI SIR S3 List of Tables Table

Page

I

Properties of the Nitroalcohols from the Literature......

5

II

Summarized Calculations for Application of the z/ashbum Correction..................................

35

cluinm»T*17.aH

rorrep.t.inff . t.nA 1 __ .... ^— - —0 At?—r -4 -j.........

37

III

1rvil a----t.ion —

IV

Summary of Data:

2°C. Benzoic Acid Standardizations.....

41

V

Summary of Data:

3°C. Benzoic Acid Standardizations.....

42

VI

Sunmary of Data:

2°C. Benzoic Acid Standardizations.....

44

VII

Summary of Data:

3-nitro-2-butanol......................

45

VIII

Summary of Data;

2-nitro-2-methyl-l-propanol............

46

IX

Summary of Data:

2-nitro-2-methyl-l,3-propanediol.......

47

X

Summary of Date:

2-nitro-2-ethyl-1,3-propanediol........

48

XI

Summarv of Data:

2-nitro-2-propyl-1,3-propaned iol.......

49

XII

Sunmary of Data:

2-nitro-2-isopropyl-l,3-propanediol....

50

XIII

Summary of Data:

2-nitro-2-methyl-l-pheny1-1-propanol....

51

XIV

Summary of Data:

2—nitro-2-methyl-3-pheny1-1-propanol....

52

XV

Summary of Data:

Tris(hydroxymethyl)nitromethane........

53

XVI

Summary of Data:

Hydrazine Hydrate..................

54

XVII

Summary of Data:

Trinitromethane........................

55

XVIII XIX XX XXI XXII

Statistical Properties of Experimental Data on Heats of Combustion...........................................

56

Summary of Results?

Heats of Combustion and Formation....

57

Heat of Combustion vs. Oxygen Balance...

62

Summary of Data?

Experimental Data for Sample Calculation of the Water Equivalent...........................................

73

Experimental Data for Sample Calculation of the Heat of Combustion.

81

LIST OF TABLES ALT) FIGURES (Cont»d.) List of Figures

Schematic Diagram of Apparatus......................

9

.•firing Diagram for Heater.......................... .

10

Wiring Diagram for Firing Circuit..................

10

The Calorimeter Assembly...........................

11

Bomb and Calorimeter Can...........................

12

Balance

and Weighing Flasks.......................

16

C: " .iT.alysis Apparatus.............................

17

Plot of Heat of Combustion vs. Oxygen Balance.......

63

Time—temperature Plot for the Initial Rating Period..

75

Time-temperature Plot for the Final Rating Period....

76

Plot of Air Temperature Minus Calorimeter Temperature vs. Time for the Experimental Period.............

73

ABSTRACT Using the adiabatic method of bomb calorimetry the heats of combus­ tion of the following compounds were determined:

3-nitro-2-butanol, 2-

nitro-2-methyl-l-propanol, 2-nitro-2—methyl-1,3-propanediol, 2-nitro-2ethy1-1 ,3-propanediol, 2-nitro-2-propyl-1,3-propanediol, 2-nitro—2-iso­ propyl-1,3-propanediol, 2-nitro-2-methyl-l-pheny1-1-propanol, 2-nitro— 2-methyl-3-*pheny1-1-propanol, tris(hydroxymethyl)nitromethane, hydrasine hydrate, and trinitromethane.

Statistical properties of the experimental

results on the heats of combustion are given in Table I, page ii. The experimental values have been corrected to the standard conditions proposed by v?ashbum(33), and assuming the applicability of the perfect gas laws, the heats of combustion at constant pressure have been calcu­ lated.

From the latter values heats of formation for the compounds have

been calculated.

A summary of the results is given in Table II, page iii.

The heats of combustion of the solid nitroalcohols have been shown to be a linear function of the oxygen balance of the molecules, and an equation has been derived which fits the data with a standard error of estimate of 41.4 cal./g.

i

-^-^lOtOO'-rHirvcO'O-J’ C'^4'f''C|r\ -I »-> -3 *J CO fO (O

3a o ©

%m

18 c c c o o o •H *H -H ■P +S -P © H O« N©

n w

■% I— 1 o c 3 -*-> 3 X> 1 cv 1 o u -t-> •H c 1 « C O -*-> © bQ c “P •rl > i? H O © > c c •rl •n © © 3 b O •rl u +-> ©

SZ

■s

D-. O a’ cu

1 4->

5

3

a, a, © x» ©

n

j ?AiO& 4>

2 »* f a BI ■© Sl . I rv cv cv cv cv CV CV

£ CV

& £ b h h

u o u c c a o o o i i i cv ro cv CO cv cv cv cv cv cv cv

ii

31

3

vO v£»

r*•\

CM

O' 'O

8

O

o

3

©1

8

C*-

-S is3co to

1.15 iA rl • H 44 rUN • O O

• UN « U un O • O 4C

8•

un

iA t o IA

un un

nO

un

O' vO 4 0 44 r0a 0 0 UN 0O

*o

a 2

w

n

u

i l l O

so.

0

h

3p .

3 I CM 4 irsl • c I ON

*

O' un

00

8• iH ■41 44 r- CM $• -34 . O' 0 0 0 0 8 UN UN c*- 00 00 CM ON . O 41 vO O• r-1 O C"-

^0• O 44 vO un • UN

ON

0

0 fe. 1 C*>

8• H ♦4 • O un to

8• H 4C C* *N C •

P• 0 4. vO c-

8 P

8 iA tn r# 0 41

CT“ C—

iA O♦ H X r»A •

8

C>

3♦ O H un

00

o

3• 1—1 +4 nO

O• & P 3• H

(A

P

O

0

3®

1O0,

0 * O4 ,

1 *

1

ON

-1 x: a. _L

i £ ex 1

i

I

Am

1

1

I0 I&O

f

tl

I CM

is •H

is •H

CM

CM

4 4 is is is‘ ii •H •H ■H f CfM CMf CM is CM

? CM 4 f

1

? iii

I

ON U\

Q CM

H

41

P•

O 41 UN O' 4

UN •

5 r—• a

o

h A

H

ON •

r -i

rH O

O O•

solid

Ji§

♦1

vO

solid

bO

41

CM ON • O 44

>0• O 44 UN H•

solid

o o

T * o

nO

iA 00

solid

UN''*. QOCM •

00

un

solid

o°i

8

590.21

i.

&

IA 4* IA

O' •

liquid

o

e*-

69*0

^r 43

un

8

07*0

S’ 8

vO Ox• O O' un

ON •

$

♦

o o •M >1 CM OUN' (A O' CO UN H

o°i

VIZ«•-io

1

C M ON •

t

f

42

V U 8* 3 “ 88 ® S r-t -^» > ©

© a +> 9 +> O 8 &§ ° •H O Q 00 U

s 00

£

&s e s

O H H b< C

PQ O

Q

12

tx « C J *■8

I S

CJ> p.

© -M

t> 5P. O »—I to Q

vj

tx

T3

s

1CQ

OS p. « P. TJ

5«> 5 r-H 5 bO

•H

•S & ZE ® >9 -2 O

1OQ OQ8

O

I

&

h A

CO

*8 -p

o fc o

o

3• R• lA °. r » a IA IA

M)

O O

n I

3• ^

1 s •H

-P> O

to

!

I■*» o

o

4

o •H U

•Jj o

V O

H

»

^

3

♦

J ■ H *8 O * 5 H o

« 4 »

o

3o

vO

8

£

o o

no

4>

* & 1 8 C O 5 m A

£

g

?

1

3 ►

& •

■ P

8

»

„

5*

cv

_

—♦ I CV

8 CV ON -3 •

§ «* ► «>0 «*

u

g.

i V* o •p

-3 -

• C*A NO

« >>

5

%h o

*s> •ft

fI

*

& cn

On

nO