Table Of ContentThis thesis, having been approved by the
special Faculty Committee, is accepted by
the Committee on Graduate Study of the
University of Wyoming,
in partial fulfillment of the requirements
for the degree of^f^C&/i.^..^.Qd^kzCL...
Chairman of the Committee on Graduate Study.
Secretary.
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The Preparation and Certain Physical Properties
of the Stearates and Palmitates
of
Caleium, Magnesium* and Zln@
by
Dorothy Lorena Barton
Thesis submitted to the Department of
Chemistry and the Committee on graduate
Study at the University of Wyoming, la
partial fulfillm ent of the requirements
for the degree of Master of Science.
Laram ie, Wyoming
1942
LIBRARY
WYOMING
UNIVERSITY OF
V ‘ LARAMIE
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UMI Number: EP19764
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CONTENTS
Page
LIST OF TABLES. ..................................................................... i l l
INTRODUCTION........................................ lv
f CHAPTER I - REVIEW OF LITERATURE......................................... 1
CHAPTER II - MATERIAL AND METHODS................................................. 8
CHAPTER H I - EXPERIMENTAL WORK..................................................... 11
Preparation of the S o a p s..................................................... 11
Testing of the Soaps.................................................................... 13
Solubility of Soaps without A gitation........................... 15
Solubility of Soaps with A gitation.................................. 18
Refractive Indices of Soap S o lu tio n s...................... 23
D ensities of Soap Solutions................................................... 24
V iscosities of Soap Solutions.............................................. 25
Surface Tensions of Soap S o lu tio n s....................... 2?
Hydrogen Ion Concentrations of Soap S olu tion s..,. 29
( ^ Colloidal Properties of the Solutions.......................... 30
CHAPTER IV - (JENSRAL DISCUSSION AND SUMMARY................... 32
BIBLIOGRAPHY............................................. 34
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i n
LIST OF TABLES
B ge
Table 1. Per Cent Ash of Soaps............................................... 15
Table 2. Solubility of Soaps in Water 1m Twenty
Four Hours without A gitation,............................... 1?
Table 3. Solubility of Soaps In Water In Two Weeks
without A gitation................. 18
Table 4. Solubility of Soaps in Water in Two Days
with A gitation. ............................................. 19
Table 5. Solubility of Soaps in Water in Fifteen
Days with A gitation. ............................................ 20
Table 6. Solubility of Soaps in Benzene.......... .............. 21
Table T. Solubility of Soaps In Anhydrous E th e r ..... 22
Table 8. Solubility of Soaps inA bsolute A lcoh ol.... 23
Table 9. Refractive Indices of Water-Soap Solutions. 24
Table 10, Relative V iscosities of Water-Soap
Solutions................................................................................ 26
Table 11. Absolute V iscosities of Water-Soap
S olu tion s..................................................................... 2?
Table 12. Surface Tensions of Water-Soap Solutions... 28
Table 13. pH of Water-Soap Solutions...................................... 29
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INTRODUCTION
Inasmuch as the stearates and palmltates of calcium,
magnesium, and zinc are used in industry in grease making,
pigment suspension, rope lubrication, cosmetic production,
wax compounding, mould lubrication, waterproofing, cement
treatment, lacquer flattin g, and many other applications,
it may be of much value to know some of the physical
properties of such compounds. A search of the literature
revealed very lit t le information on the subject although
there was much recorded about soluble soaps. The stearates
and palmltates of calcium, magnesium, and zinc are listed
in the literature as “insoluble” soaps. But because of
differences in appearance of several water-soap mixtures
that were standing at room temperature, it was thought that
they would evidence some slight measurable solu b ility.
Possibly the same thing would be true of other solvents.
Therefore, these experiments were undertaken to determine
the solu b ility of the so-called “insoluble” soaps in water,
ether, benzene, and alcohol. And if there were any
material dissolved in these various solvents, the densities,
surface tensions, refractive indices, and v isco sities of
the solutions would probably deviate from data obtained
for the pure solvent and the deviation might be enough
to be of some significance.
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A convenient laboratory method for the preparation
of such soaps was sought. Since the soaps were ”Insol
uble” , the method would d iffer in some respects from
those ordinarily used to make "soluble" soaps. Since
fatty acids or fats of relatively high purity would be
the expensive Item on the lis t of reagents needed, it was
necessary to develop a method of preparation of the soaps
that would make use of such reagents without waste. The
pure saponifying agents are comparatively Inexpensive.
Since some of the results obtained differed somewhat
from the rare b its of data found in the literatu re, a
satisfactory explanation of the apparent irregularities
was sought.
At this time the writer wishes to take the opportunity
to thank Dr, Fred Freytag, who directed this research,
for his interest and many helpful suggestions during the
progress of the work.
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CHAPTER I
REVIEW OP LITERATURE
Ira spite of the many uses for the stearates and pa Im
itates of calcium, magnesium, and zine, as pure soaps and
as mixtures, there is an unusual lack of information on
the pure compounds as revealed in the literature. A few
workers have prepared the soaps and each seemed to have a
special method of his own. Wore information could be ob
tained on the preparation of the soaps than on their
properties.
There are some brief accounts of the preparation and
analyses of the m etallic stearates and palmltates in Chev-
1 2
reul*s "Les Corps ©ras" and in Llebig*s Annalen,
3
Cady and Llchtenwalter prepared some silver, copper,
lead, and barium soaps. They treated the acids with a slight
excess of sodium hydroxide and then added theoretical a-
mounts of the m etallic sulfates or acetates. The heavy
metal soaps were purified by washing with water.
4
Koenig prepared the stearates and palmltates of cop
per, chromium, eadmlum, iron, manganese, mercury, nickel,
lead, and tin. He added a quantity of fatty acid to a
1. Chevreul, M. E ., Recherches chlmlques sur les corps
gras d*orlglne animate, Strasbourg et Paris, Levrault,
2. Ann.* 3£t 51 (184©); 26, 44 (184©); 84, 297 (1851);
88, 29o (1853).
3. Cidy, H. P., and Llchtenwalter, R. © ., J. Am. Chera.
Soc., 1434- 144© (1913).
4. Koenig, A. E ., J. Am. Chem. Soc., 2j£, 951-961 (1914).
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2
lit t le less than its stoichiom etric equivalent ©f 0.5 $
sodium hydroxide solution In a flash with a reflux con
denser and heated the mixture on a steam hath for 10-12
hour®. The globules of excess fatty acid in the otherwise
clear solution were removed hy means of filterin g thru
cotton. That prevented the formation of basic salts later
in the procedure. 15 g. of the dried sodium soap was d is
solved in a lite r of warm water, yielding a clear solution.
A cloudy solution was obtained if the soap were dissolved
In cold water and then warmed. The solution was poured,
with stirrin g, into a 1%' solution of the heavy metal
chloride or sulfate. The precipitated soaps thus formed
were washed by decantation until the liquid was found
to be free of soluble sa lts. The soaps were dried at
115® to 120® "0. for 10-12 hours.
5
In studying the solu b ility of his soaps Koenig placed
a portion of the finely powdered salt in a test tube and
shook it with a few cubic centimeters of the solvent.A fter
several hours a portion of the liquid was evaporated on a
watch glass. The soaps were recorded as soluble (1# or
more), slig h tly soluble (a few hundredths of a per cent),
and insoluble.
fie found that the soaps did not have a well defined
6 0 &
melting point , having a range of 2 -10 on the centigrade
scale. However, the crystalline compounds with pyridine
of solvation had very sharp melting points.
5. Ibid , p. 954 .
6. Tbtd. , p.<
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