The Molecular Structure of Carbon-Suboxide

143 Pages·8.086 MB·English

by  Hall, Wade E

TEE MOLECULAR S M S CF CAEBON SUBOXIDE
by
Wade Eckes Hall
A dissertation submitted In p artial fulfillm ent of the
requirements for the degree Doctor of Philosophy
in the Department of Chemistry In the
Graduate College of the State
University of Iowa
August 1951
ProQuest Number: 10666196
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ACKNOTLEDSEMBm
The w riter wishes* to express h is appreciation to
Dr* Seorge Evans who suggested the problem; to Dr* George
Glockler who assisted in its development as the w riter fs
advisor; to Dre* Henry T* Hoffman and Powell A* Joyner, who
were always w illing to lend a helping hand when on© was
needed; and to h is w ife, for encouragement, and assistance
with the typing of th is papen
U i
TABLE OF CCKTBSTS
Chapter page
X Introduction # » • « * « • # * 1
H isto rical background * « « * * I
Statement of the problem » • • • 4
IX Experimental Procedure » « * « • » 7
Instrum entation • * # * * * 7
Operating procedure * « • « 0
Zero sh ift * » • « * « 12
Spectrometer testin g procedures * 13
Excessive noise and its reduction » 15
Boise of in tern al origin * * 15
Boise of external origin * • IS
S ells ■ • t' # * • # # • Si
© election of c e ll window m aterial • 25
Preparation of c e ll windows • . 27
f&euum tig h t cement and wax • * 31
Preparation of carbon suboxide * *. * 32
111 Summary of the Bate * * * * « * ♦ 40
I f Discussion of the Theory * . * • * 49
BcraSal vibrations of carbon suboxlde , 53
V Mathematical Treatment » • « « * * 65
©enelopment of method of Duncan & Collar 65
A pplication to systems Involving
free vibration « • • • 71
Appiicati on to lin ear iltg* COg 85
A pplication to systems or restricted
movement « « « » , 98
A pplication to bending vibraU ons . IQ*
VI Discussion of Carbon Suboxide Molecule . . 113
Unear X3Y2 . 117
Cis-bent Xg®2 . . . . . . 125
VII Summary ...........................................131
Bibliography . . . . . . « 133
Biography . . . . . 136
iv
f ABIE OF JttOPBJM
m *
Fig* 1 toeelM # models of carbon suboxi&e 5
fig* a Diagram of time clock c irc u it * * * 11
fig* 3 Diagram of glass c e ll used to control
the temperature of the sample * » » 82
Fig* 4 ■Suggested c e ll for controlling the
tem perature of the sample * * • 25
Fig* 5 Apparatus fo r production of carbon
subemide according to method of Hurd
and Pilgrim * * * * 37
Fife* e
Hormal vibrations of lin ear model of
carbon suboxide * * * * * * 64
Fig* 7 Hormai vibrations of oia bent model,
according to Hersfeerg • « * * • 55
Fig* 8 Corrected normal vibrations of cis
bent model of CgGg * * * » 56
V
m
TABUS TABLES
Tablft page
I V ibrational frequencies of carbon sub ox Ida
as calculated from the u ltra v io le t spectrum 43
IX The Eaman spectrum of carbon suboxid© 43
XIX The Infrared spectrum of carbon suboxide as
reported by lord and Wright 44
Vf 'The Infrared spectrum of' carbon aubo&lde a®
determined w ith N&G1 prism only 40
The Infrared spectrum of carbon suboxide as
determine# w ith I1F, l a d and XBr prisms 46
VS The stronger infrared spectrum of aliens 47
VII The stronger Infrared spectrum of
aeetaldehyde 47
VXXI The stronger Infrared spectrum of beten© 48
IX The stronger infrared spectrum of acetic acid 43
X Assignment of the fundamental vibrations of
carbon suboxide according to the lin e ar model 180
XI Assignment of the fundamental vibrations of
carbon suboxide according to cis bent model 180
XII Assignment of vibrational frequencies of
carbon suboxide according to lin ear model 184
XXII Assignment of vibrational frequencies of
carbon ouboxide according to cis~bent model 130
iri
m m um
Page 50, beginning at lin e IS, the f ir s t para­
graph of 11 procedure for rebuffing windows* should read*
If the condition of the window w arrants i t ,
grind w ith 600 mesh carborundum and @5# alcohol u n til the
window is frosted but smooth, using a polishing cloth re­
served for the purpose* Reduce the fro stin g from the
above grinding by grinding w ith alumina and 95# aLcohol.
At th is time the m aterls!begins to appear translucent;
however, one cannot yet make out small objects through It*
X
Chapter I
XMRtiDOOflQK
Carbon suboxide polymer appear® bo have bean
f ir s t prepared by Bro&le {/£} in 1873 who found that: when
carbon monoxide was passed through an e le c tric a l discharge
oar bon dioxide and a rod In’own aolid wore formed* Analysis
showed the m aterial to bo composed of carbon and oxygen,
but d ifferen t samples gave- d ifferen t compositions* Brodie
reported two mid©®* 0^0^ and 0^0^. II® suggested th at
a series of oxocarbon® sim ilar to the aerie® of hydrocarbon®
might exist*
th is work was repeated and confirmed by Berthelot
C /*) who found fu rth er that th® brown oxide upon heating .gave
carbon dioxide and C^O^* Be thought that the follow ing
reactions occurred*
n CO -— » Cn0n
Gn°n -----* °n~l°jv*2 °°2
Further loss of COg, in a sim ilar manner, from the compound
w ith n = 2d leads to C^gOg* B erthelot ( /^) also found some
evidence to Indicate th at the f ir s t member of the series
might exist*
2
The next major development occurred in 1906 when
p le ls end Wolf ixt} accidentally prepared a gas, CgOg* upon
heating diethyljaalonate w ith phosphorus pent oxide# They
named th is gas carbon suboxide. I t is th is substance which
Is usually referred to as carbon suboxide today, although
there were objections to th is name since many thought th at
the term shofid refer to the class of oxides having fewer
atoms of oxygen than carbon rath er than to an Individual
compound (40)*
A number of workers have since prepared carbon
suboxide from various compounds (20, ¥J, * zn } m )* i t
appears that the method of Kurd and Pilgrim (t-7) IS the
most practical*
constitution of CgOj boo given r i.e to conoid-
arable controversy* P iels and Wolf {*/} believed i t to be
lin ear 0=0 *0=0-0 and gave the equation for its manufac­
ture as
eHg(C000gSg)8 —5. 3 c2h4 +- 2 HgO + cso2
Mieheal <fV) thought i t would be possible to
decompose diethylmalonat© so as to get a cyclic compound
0
/ \
G 0 = 0
3
P iels attem pted to show on the basis of the
boiling point (w) sad m olecular refractio n {/?} th at the
lin ear structure was correct but Michael (3*1 refuted him*
Staudinger and Klever {&) considered the gas a
diketene and prepared i t accordingly.
Kedgrove (39} has calculated the molecular heats
of combustion and of form ation according to the lin ear
and cyclic form ulas, but no data are available for compar­
ison,
LeFevre and LeFevre (3/ ) determined the dipole
moment of carbon suboxide and found i t to be 0,7 debye.
They calculated th at the cyclic form should have a moment
greater than 3 debye and th at the lin ear form should have
a vanishingly sm all dipole moment# This moment of 0*7
appeared too large fo r the possible experim ental erro rs,
including polymerisation* They pointed out th at the
course of many addition reactions indicated th at at least
part of the molecules had an electronic structure which
should have a small dipole moment*
Broekway and Pauling ( 77) have determined the
electron d iffractio n images and conclude th at the molecule
Is linear* Boersch (/r) disagreed w ith Brockway and
Pauling claim ing th at the Images which he obtained could
b etter be Interpreted on the basis of M ieheal^ (3Y) cyclic