Table Of ContentTHE HEATS OP COMBUSTION
OP SOME AMIDES AND AMINES
A Thesis
Submitted to the Faculty
of
Purdue University
b y .
William C, Dsombak
In Partial Fulfillment of the
Requirements for the Degree
of
Doctor of Philosophy
August, 1950
PURDUE UNIVERSITY
THIS IS TO CERTIFY THAT THE THESIS PREPARED UNDER MY SUPERVISION
William C • D&ombak
by
THE HEATS OF COMBUSTION OF
entitled
SOME AMIDES AND AMINES
COMPLIES with; the university regulations on graduation theses
AND IS APPROVED BY ME AS FULFILLING THIS PART OF THE REQUIREMENTS
FOR THE DEGREE OF
__________ Doctor of Philosophy ________________ _
Professor in Charge of Thesis
TO THE LIBRARIAN:—-
THIS THESIS IS NOT TO BE REGARDED AS CONFIDENTIAL.
PHOFESBOB TK OHABGE
GRAD. SCHOOL FOBM O—3.40—1M
ACKNOWLEDGMENT
The author wishes to acknowledge the warmth and
consideration he has received from Dr. Herschel Hunt, the
director of this research, with whom it has been a pleas
ure to work, and to express, to Dr. E. T. McBee, apprecia
tion for the special assistance he rendered in securing,
from the Purdue Research Foundation, the financial support
which permitted the investigation to proceed without inter
ruption.
TABLE OB1 CONTENTS
Page
ABSTRACT............................................. i
INTRODUCTION ......................................... 1
EXPERIMENTAL......................................... 3
Method . . . . . . ...................... . . . 3
Apparatus ........ . . . . . . ................ 5
Preparation and Purification of Reagents........ 10
Procedure.................................. 16
Calculations • 24
Units and Standards............................ 31
Results • • . . « . . • • • • • • • • • * . • • • 32
DISCUSSION OF RESULTS................................. 56
SUMMARY............................................... 54
BIBLIOGRAPHY ............ 65
VITA
LIST OF TABLES
Page
1. Data for the Heat Capacity of the Calorimeter*.... 33,34
2. Data for the Heat Capacity of the Calorimeter..... 35,36
3. Data for the Heat of Combustion
of Sallcylaldoxime.••••• 37,38
4. Data for the Heat of Combustion
of p-Dimethylaminobenzaldehyde • . . 39,40
5. Data for the Heat of Combustion
of 3-Hydroxy-2-naphthoic Acid...... 41,42
6. Data for the Heat of Combustion
of 2,6-Diaminopyridine.•••••• 43,44
7. Data for the Heat of Combustion
of n-Propyl carbamate•••.••• 45,46
8. Data for the Heat of Combustion of Pentanamide. . . . 47,48
9. Data for the Heat of Combustion of Hexanamide...•• 49.50
10. Data for the Heat of Combustion of Octanamide .. . . • 51,52
11. Data for the Heat of Combustion
of 3-N-Phenyl amino-2-naphthoic Acid...... 53
12. Data for the Heat of Combustion
of 4,7-DUceto-5,6-dlaza-decanedioic Acid.... 54,55
HEATS OP COMBUSTION VI.1
THE HEATS OP COMBUSTION OP SOME AMIDES AND AMINES
* 'A
By William C* Dzombak and Herschel Hunt
(Department of Chemistry and Purdue Research. Foundation
Purdue University. Lafayette. Indiana.)
AN ABSTRACT
The Heats of combustion have been evaluated for some
organic compounds which contain nitrogen. The apparatus and
the experimental procedure employed for these measurements
have been described In previous communications (1,2,3) from
this laboratory. Using the ordinary, non-adiabatic method of
calorimetry, the heat of combustion has been determined for
each of the following compounds: pentanamide, hexanamide,
octanamide, sallcylaldoxime, n-propyl carbamate, 2,6-diamlno-
pyridlne, p-dimethylaminobenzaldehyde, 3-hydroxy-2-naphthoic
acid, 3-N-phenylamino-2-naphthoic acid and 4,7-diketo-5,6-
diaza-dec&nedioic acid.
The energy equivalent of the calorimeter was deter
mined with benzoic acid, Standard Sample 39g, obtained from
the National Bureau of Standards. Cylindrical pellets of all
of the compounds were formed. In some cases, a wafer of
1 This article Is an abstract of a thesis submitted to the
faculty of Purdue University by William C. Dzombak In
partial fulfillment of the requirements for the degree of
Doctor of Philosophy.
benzoic acid was placed above the pellet, In order to promote
ignition, or below the pellet. In order to prevent the forma
tion of the alight deposit of oarbon often found in the Igni
tion cup before this measure waa taken. The weights of the
pellets were adjusted so' that the amount of heat liberated was
comparable to that liberated by the burning of the 1.075 +0.02
gram of benzoic acid employed for each calibration experiment.
Stainless steel crucibles, pre-lgnlted to provide a clean and
reproducible surface, were employed to contain the pellets.
The Parr double—valve oxygen bomb used has a volume of 0.358
liters. The ignition cup and 1.1 ml. of water were placed In
the bomb, and the bomb was filled with oxygen to a pressure
of 30 atmospheres, absolute, at 25°C.
Temperature measurements were made with two nine-
junction copper-constantan thermels and a White double poten
tiometer These observations were made, during the 60-minute
test period, at 1-minute intervals sounded by a timer (3) mod
ified by Klbler (4) to operate from the beam of light reflect
ed from a mirror mounted on the shaft of a synchronous elec
tric motor.
The energy liberated by the ignition of the fuse
wire was evaluated in the manner previously described (2).
Details concerning the treatment of the experimental
data have been presented in other publications (1,2). The
weights of all of the samples were corrected to vacuum.
The values for the heats of combustion listed are
to be referred to the process which occurs at constant vol
ume and at 25°C to produce gaseous carbon dioxide, gaseous
nitrogen and liquid water.
COMPOUND HEAT OP COMBUSTION
kg.-cal./mole
Pentanamlde 754.56 + 0.25
Hexanamlde 905.83 +0.18
Octanamlde 1218.5 + 0.2
Sal 1cylaldoxime 854.03 +0.16
n-Propyl carbamate 551.41 + 0.10
4,7-DIketo-5,6-diaza-decanedioic acid 846.01 + 0.49
2,6 -DIaminopyr idlne 708.10 + 0.11
3-Hydroxy-2-naphthoic acid 1177.6 +0.2
3-N-phenylamino-2-naphthoic acid 1980.4 + 0.5
p-Dlme thyl amlnob enzaldehyd e 1189.0 +0.2
The standard deviation of each value has been
reported as recommended (5) by Rossini and Deming.
iv,
REFERENCES
1. Miles, C, B. and Hunt, H.t J, Phys. Chem•, 45, 1546 (1941)
2. Millar, A, J# and Hunt, H,: J, Rhys, Cham,, 49, 20 (1945)
5. Sullivan, M, V, and Hunt, H.: J, Fhys, Colloid Cham,,
53, 497 (1949),
4. Kiblar, G, M., Eb.D. Thesis, Purdue University, Lafayette,
Indiana,
5* Rossini, F, D, and Doming, W« E,, J, Wash, Acad, Sci,,
29, 416 (1939),
