LOW TEMPERATURE HEAT CAPACITY OF SODIUM PALMITATE

AND RELATED COMPOUNDS

ABSTRACT OF

DISSERTATION

Presented in Partial Fulfillment of the Requirements

for the Degree Doctor of Philosophy in the
Graduate School of The Ohio State
University

By

John Walter Droege, A.B.

The Ohio State' University

1953

Approved by:
 i

ACKNOWLEDGEMENTS

The author wishes to acknowledge his great debt to the many

who have given freely of their time in aiding him in this research.

Only a few of them can be mentioned here.

Dr. Henry E. Mirth was the adviser during the early stages

of the work. His interest has continued undiminished throughout.

Through the kindness of Dr. Herrick L. Johnston, who also acted as

adviser for a short time, the work was carried out in the Cryogenic

Laboratories of The Ohio State University, Dr. William J. Taylor

has kindly agreed to act as adviser during the latter stages of the

research.

Mr. Nathan C. Hallett, Mr. Eugene G. Kerr, and Dr. J. H. Hu,

of the Low Temperature Calorimetry Group have been most helpful,

as has Mr. Lester A, Cox, Foreman of the Cryogenic Machine Shop.

Dr. F. B. Rosevear and others of the Proctor and Gamble Company

have kindly assisted by providing materials and carrying out X-ray

analyses.

In conclusion, the author vrauld like to mention the cooperation

of Dr. John H. Wood i-d.th whom he has been associated throughout much

of the course of this investigation. He also vhLshes to remember

the help from and the spirit of comradeship with all those who have

worked with Dr. %'firth on the many aspects of the soap problem.

933326
 11
TABLE OF COWTaj TS

I Introduction

(1) Background ------ 1

(2) Methyl Palmitate - - - - - - - - - - - - - --- - - - - - 4

(3) Palmitic Acid - - - - - - - - - -- - - --- - - - - 5

(4 ) Sodium Palmitate - - - - - - - - - - - - - - - - - - - - 6

II Preparation of Materials

(1 ) Preparation of Methyl Esters - - - - - - - - - - - - - - 9

(2 ) Distillation of Methyl Esters - - - - -- - - - - - 1 0

(3) Preparation of Palmitic Acid - - - - - - - - - - - - - 16

(4 ) Preparation of Omega Sodium Palmitate - - - - --- - - - 1 7

(5) Preparation of Delta Sodium Palmitate - - - - - - - - - I S

(6) Purity Determinations - - -- - - - - -- - - - - - - - I S

III Experimental Procedure and Data

(1) Heat Capacity Determinations - - - - - -- - - - - 22

(2 ) Methyl Palmitate - - - - - -- - - - - - - - - - - 2?

(3) Palmitic Acid - 2S

(4 ) Omega Sodium Palmitate - - - - - 29

(5) Delta Sodium Palmitate- - - - - - - - - -- - - - - 2 9

IV Discussion of Heat Capacity Data

(1 ) Accuracy - - - - - - - - - - - - - - - - - - - -45

(2) Methyl Palmitate ---- 46

(3) Palmitic Acid ----- - - -4S

(4 ) Sodium Palmitate - - - -49

 Ill

TABLE OF CONTENTS
(continued)

V Entropy Differences and Structure

(1) Crystal Structure - - - - - -- - - - - - - - - - - - - 50

(2 ) Entropy Differences - - - - - -- - - - - - - - - - $1

(3 ) Suggestions for Future Work --------------------------59

VI Summary --- - - -62

VII Bibliography - -- --

VIII Autobiography - - - - - - - - - - - - - - - - ---- - - - - — 65

 I. INTRODUCTION

(l) Background

The polymorphism of soaps and other long-chain compounds is

one of their most significant physical characteristics. Several

years ago Dr. H. E. Wirth organized a program of research at this

university to attack the problem by several different methods. With

the present work and that of G. W. Mays (l) this program has now

come to a close.

Mays has studied the dielectric constant of palmitic and

stearic acids and their methyl esters, all in the vicinity of their

respective melting points. For each acid he obtained reproducible

values for the liquid, but found that the value for the solid varied

greatly depending upon the conditions under which the sample was

solidified. Rapid solidification resulted in a dielectric constant

somewhat higher than that of the liquid, while slow solidification

gave a much lower value. He attributed this to the growth of

crystallites resulting, in the latter case, in a more oriented sample.

The methyl esters likewise gave reproducible results in the liquid

range. The dielectric constant of the solids was time dependent.

It appears that, upon solidification each of thèse methyl esters

forms a metastable phase vhich changes to another phase. This change

requires about two days, and is followed by a further transition into

a third, presumably stable phase. This latter change is indicated by

a very slight drift downward in the dielectric constant, continuing

for at least six weeks,
(2 )
¥. W. Wellman investigated three aspects of the phase

nature of sodium palmitate using dielectric constant techniques. He

prepared cakes of hydrous beta and delta sodium palmitate varying in

water content from one to four percent, and found that the dielectric

constant curve showed a sharp break upward at three percent water.

This tends to confirm B u e r g e r c l a i m that these phases exist as

hemihydrates. Thiessen and co-workerl^^found a transition which they

called ’’genotypic" at a temperature corresponding to the melting point

of the parent acid. In an attempt to reproduce these results, Wellman

investigated the dielectric constant of omega and Iij^lrous beta sodium

palmitate as a function of temperature. He found no evidence of the

’’genotypic" point until he added 5% palmitic acid to his sample, in

idiich case he obtained a curve somewhat similar to that reported by

Thiessen. Finally Wellman followed the dielectric constant of a

sample of omega sodium palmitate during heating to 207“C. He found

transitions at 117.8°, 137°, 162°, and 206° for the phase changes

previously reported by Void, Rosevear, and Ferguson^^^by Void and

Vold^^'^*^^ and by Chesley^*^^

G. T. H e w i t t d e v i s e d a piezometer for measuring the change

in volume of samples under pressure. He used his equipment for deter­

mining the effect of pressure up to 15,000 Ib./sq. in. on the melting

point of palmitic acid and on the phase boundries of the system sodium

palmitate - water. He found the transition temperatures to be raised

by increasing pressure, the effect being greater for less hydrous

 3
samples. He found that these rather sluggish transitions occurred

much more rapidly when the pressure was changed at constant temperature

than when the temperature was varied at constant pressure. No change

in the number of phases was found at higher pressures.

W. L. Kosiba^^^^ constructed a torsion balance inside a thermo-

stated vacuum system vri.th an accurate manometer for determining the

vapor pressure of hydrous sodium palmitate phases. He found sharp

breaks in the isothermal vapor pressure curves for beta, delta, and

alpha sodium palmitate at about 3.1^, corresponding to the hemi-

hydrate composition. He calculated the heat of wetting above this

composition and the heat of hydration of the hemihydrate. At lower

water contents the curves did not exhibit the flat portion expected

for the equilibrium between anhydrous salt and hydrate. Kosiba

concluded that this region represents a solid solution, as had been

stated by Nordsick, Rosevear and Ferguson (12 )

(13)
J, H, Wood determined the heat capacity of anhydrous beta

sodium palmitate and of three hydrous beta samples of water content

2.5^, 3.0^» and 4 . ^ . He foxand a heat effect at the ice point only

in the last of these, thus agreeing with the conclusions of Kosiba

and Wellman concerning the existance of a hemihydrate. However he

found a anomalous heat effect over the range 140“ to 280“ K, This he

attributed to some sort of co-operative rearrsingement «

The present investigation was designed to extend the heat

capacity work of Wood to provide thermodynamic information concern­

ing other sodium palmitate phases as well as the related compounds

palmitic acid and methyl palmitate. It was also of interest to find

 4
whether any phase changes might occur in these compounds below room

temperature.

(2) Methyl Palmitate

Garner and coworkers have carried out a series of studies of

the specific heats and heats of crystallization of long chain com­

pounds. Using a sample with a setting point of 29.05°, King and

G a mer found for the specific heat of the solid, 0.43Ô cal./deg,/gm;

for the heat of crystallization, 13.23 Kcal./raolej and for the

specific heat of the liquid, 0.524 cal./deg./gm. They used the method

of mixtures which gave the difference in heat content Wien the sample

was dropped from a thermostat into a colder calorimeter. Specific

heats and the heat of crystallization were then obtained by subtraction.

Their value for the solid was thus the average specific heat over

the temperature range 18® to 24°C. and their value for the liquid

was the average for the range 36® to 59®C. They observed a consider­

able amount of scatter in their data for the solid. They attributed

this to the fact that methyl palmitate crystallizes very slowly.

Many attempts have been made to determine the temperature at

which solid and liquid methyl palmitate are in equilibrium. The

results have been inconclusive, showing marked dependence on the

method as well as on the purity of the material. The solidification

of molten methyl palmitate does not show typical behavior. After

supercooling, the temperature rises continuously until the sample is

almost completely crystallized. The maximum temperature observed

in such an experiment has been called the "setting point". Francis

and Piper^^^^ have compared the setting points of many compounds with

the "melting points" and "resolidification points". Their melting

point vjas the temperature at viiich a small amount of the solid on

the side of a 3 mm. tube was observed through a telescope to begin

to melt. Their resolidification point was the temperature at which

a small partly melted sample was observed to begin to resolidify.

For methyl palmitate Francis and Piper reported a setting point of

29.20®C. and a melting point of 30.55°C. They stated that the beta

phase, obtained by crystallizing the melt, changes over to the more

stable gamma phase, which is characterized by a higher melting point.

They reported that their setting point was for the beta modification,

that they were unable to obtain a beta melting point, and that the

melting point they observed was for the gamma phase.

Guy and Smith^^^^ have introduced still another indication of

the transition point. Their "clearing point" is the temperature at

which the sample loses its cloudy appearance on heating. They re­

ported a temperature of 29.55"C. for the clearing point of methyl

palmitate.

As reported above. Mays seems to have observed tivo phase

transitions occurring in recently solidified methyl palmitate.

This complex polymorphism vjould account for the difficulty in deter­

mining the equilibrium melting temperature.

(3) Palmitic Acid

Francis and Piper' in their extensive work on long-chain

compounds, have listed the folloivlng values for the melting point of

palmitic acid: Setting point, 62.60®C; resolidification point.

 6

62.A”C; melting point, 62.9“C, These are for the stable "C” form,

which is obtained upon crystallizing the melt,

C16)
Guy and Smith purified a sample of palmitic acid by a total

of twenty-two recrystallizations from various solvents. They found

a melting point of 62,76*0. and a freezing point of 62.74*0.

f17')
Ward and Singleton ' have recently determined the specific

heat and heat of fusion of palmitic acid. Their specific heat

results for the solid are reported below with those of Parks and

Kelley and with the results of the present investigation in Table 5

and are plotted in Fig. 4- Ward and Singleton reported a setting

point of 62 ,75*0 . and a calorimetric melting point of 62.58*0.

The only extensive heat capacity work done previously on

palmitic acid was that of Parks and K e l l e y ^ v i i o made determina­

tions over the range 90° K to room temperature. They used the iso­

thermal method, with procedures similar to those used in this research.

(4 ) Sodium Palmitate

With the exception of Wood’s work on beta sodium palmitate dis­

cussed above, no low - temperature research on an^r of the phases of

sodium palmitate has been reported. A number of distinct phases

have been reported in anhydrous sodium palmitate above room temperature,

not to mention the complex and controversial soap-water diagram.

Void, Rosevear, and Ferguson^identified the omega phase,

which appears upon cooling an anhydrous sample from about 120®C or

higher. This phase had been called gamma by de Bretteville and

McBain^^°\
 The delta phase, reported by Ferguson, Rosevear, and S t i l l m a n ,

is the phase usually obtained upon room temperature dehydration of a

hydrous sample. Delta appears to be the stable phase in samples

containing more than about five percent water.

Beta is the phase of greatest prominence in commercial soaps.

It is obtained by mechanical working of a hydrous sample at about

80°C. It appears that complete dehydration of a beta sample at room

temperature results in at least partial transformation to delta.

Wood's calorimetric studies of the beta phase have been discussed

above.
The phase changes occurring when anhydrous sodium palmitate

is heated have been studied by several methods. Void, Rosevear,

and F e r g u s o n ^ u s e d visual observation, dilatometers, and the

(7,8)
polarizing microscope with hot stage. Void and Void , also used

dilatometer and polarizing microscope. Their microscope stage was

equipped with a hot wire, so that the sample could be observed over
(oA
a range of temperatures. Chesley''" used X-ray techniques to

characterize the phases. Vold^^^ carried out some differential

heating and cooling runs, by means of which he was able to estimate

the heat effects accompanying some of the phase changes. Wellman's

dielectric constant work up to 207°C. has been mentioned previously.

At about 117.5“C., omega is transformed into the "subwaxy"

phase. This is changed to "waxy" at 137“C, Vold^^^ observed a

change to "superwa^" at about 172“G. by the hot wire technique,

(2 )
Wellman obsei-ved an ill-defined break in his dielectric constant

curve at about 162“C. It cannot be said that the existance of this

 s
’’supervraxy" phase has been well established. The next change,

to "subneat," occurs at about 207“C. The "subneat" to "neat"

transition was observed visually and dilatometrically at 255"C, but

Void
(6) found the heat effect to take place at 237®C. The final

transition, to isotropic liquid, occurs at 295°C.

Void’s values for the heat effects are as follows:

crystal to subway: 4.8 Kcal/mole,

subwaxy to waxy: 3.9 Kcal/mole,

superwaxy to subneat: 1.8 Kcal/mole,

subneat to neat: 1,5 Kcal/mole,

neat to isotropic liquid: 0.5 Kcal/mole,

These values are probably in error by ten to twenty percent.

 II PREPARATION OF MATERIALS

Fatty acids are comironly separated and purified by lovr-

temperature crystallization from solvents and by fractional dis­

tillation at reduced pressures. The former method is especially

useful in obtaining unsaturated acids. The latter was selected

for this research. Methyl esters were used rather than the acids,

since the esters have lower boiling points.

(l) Preparation of Methyl Esters

Starting materials were 1000 grams of Eastman Palmitic Acid,

560 grams of Armour Neofat S, and 85OO grams of Proctor and Gamble

Triple Pressed Stearic Acid, These materials contained about forty

to seventy percent palmitic acid. 1800 grams of the starting

material were refluxed for about a day with 3400 ml. methyl alcohol

and 75 ml sulfuric acid. About five liters of hot water were added

to the flask. This caused a separation into two layers. The lower

layer, containing most of the alcohol, water and acid, was siphoned

off and discarded. The ester layer was dissolved in a low-boiling

petroleum ether and treated v/ith dilute sodium hydroxide to

precipitate unreacted acid. The solution was then filtered, and the

filtrate acidified with dilute sulfuric acid and washed with water

until free of acid. The petroleum ether was boiled off under vacuum.

The esters were hydrogenated at about 1S0“C. using a Raney

nickel catalyst. After hydrogenation the Iodine number was found to

be less than 0.2. This indicates the virtual absence of unsaturation.

 10

(2) Distillation of Methyl Esters

A distillation column -was built for the fractionation of the

methyl esters. It was patterned after the design of Weitkamp and

(22)
Brunstrum^ . A low pressure drop was achieved by the use of

Stedman packing. The heating coils were so situated and controlled

as to give nearly adiabatic conditions along the column. Contamina­

tion of the product by stop-cock grease was minimized. A closely

regulated manostat kept the pressure nearly constant. The take-off

assembly was designed so that small samples could be collected and

characterized.

The material to be distilled was boiled in one liter or t-wo

liter flasks, some of -i\rinich had re-entrant thermometer wells. Glass

mantle heaters controlled by variable transformers were used. The

flasks were connected to the fractionating column by means of a ball

and socket joint lubricated vdth high-vacuum silicone grease.

The fractionating column was a four foot length of 25 mm. O.D,

(23)
pyrex tubing. The packing, modeled after that of Stedman and

W e i t k a m p ^ w a s fabricated from 40 x 60 mesh monel screen. The

screen -was cut into one inch diameter circles with a punch press.

One-half inch sectors were cut from the discs. Packing units were

each fabricated from two such discs. The lower member was bent

into a cone, concave up-ivard, so that it would just fit inside the

column. A one—half inch sector was bent upwards so as to form a

verticle baffle in the finished unit. The upper member was bent into

a similar cone, but concave downward. A one-half inch sector was bent
 11

upward, but on the side of the opening opposite to that on which the

baffle on the lower member was formed. In order that this upper

baffle might fit along the column wall a segment was cut off and

discarded. The two pieces were silver-soldered together with the

vertical baffles in line. Two such units were then silver-soldered

together to form a rigid section that would hold its shape in the

column. Mien the column had been filled with these sections, the

result was a series of cones having holes on alternate sides of a

one-half inch vertical baffle running the length of the column. This

provides a very long path for the ascending vapor, but with a low

pressure drop.

The fractionating column was held inside a length of 54 mm.

pyrex tubing wrapped with nichrome ribbon. The ribbon, which had a

resistance of 1.43 ohms per foot, was wrapped around the tube with

1/4 inch spacing. Three strips of asbestos tape running the length

of the tube beneath the ribbon helped keep it in place. The heating

coils were in four sections, individually controlled with four

rheostats and two powerstats. Fastened to the outside of the

fractionating column and to the inside of the tubing carrying the

heating coils were four pairs of thermocouples, located at the centers

of the four heating coils. These were connected through a switch­

board to a galvanometer, so that the difference in temperature be­

tween the column waD.l and the heating wall could be noted. The

galvanometer had a sensitivity corresponding to 0,05 degrees per mm.

Enclosing the vhole assembly was a third concentric glass tube,

of 75 mm. outside diameter. The three tubes were spaced by ivrappings

 12

of asbestos tape dipped in water glass. These spacers, at the top

and bottom of the column, served well to cement the whole structure

together.

The take-off assembly and pressure regulating devices are

shown in Fig. 1. A re-entrant thermocouple well in the top of the

column did not prove useful since it was found necessary to wind

this part of the assembly with an auxiliary heating coil to keep the

emerging vapor from condensing before reaching the take-off valve.

The condenser was found to be unnecessary for cooling methyl

palmitate. "A” was a length of glass tubing sealed at the bottom

to a piece of glass rod. This rod was ground to fit a valve seat

below the condenser. An iron core was sealed into the upper end of

the tube. Around the outer tube at "B" was a solenoid for raising

and lowering the take-off valve. The timing circuit is shown in Fig,2,

The length of time that the valve remains up or down was regulated

by the variable resistors "EC, The power supply providing 24 volts

D.C. is not shown.

The stop-cock through idiich the product passed on its way

to the receiver was lubricated with high-vacuum silicone grease.

Receiving flasks were connected by means of standard taper joints

lubricated with the product. The trap wa.s connected to the system

by standard taper joints, so that it could easily be disconnected

and emptied.

The manometer, "G" (Fig. 1), was filled with mercury. The

side arm had a pitch of one to ten so that the pressure could easily
be read to l/lO mm.
Fractionating
Column

To pump
 14

Figure 2.

A 110 volts, 60 cycles;

B RCA 2051;

C 5000 ohm power resistor;

D 5000 ohm grid resistors;

E 10 megohm potentiometers;

F 4 m f d. condensers;

G 8 m f d. condensers;

H Switch for opening valve manually;

I To D.C. supply and take-off solenoid.

 15
The pressure regulating device, "D", contained mercury. Two

platinum - to - glass seals admitted leads, one making continuous,

the other intermittent contact with the mercury. To set the regulator,

both stop-cocks were opened until the pressure fell to the desired

va].ue. The right-hand stop-cock was then closed, enclosing gas of

the desired pressure in the right-hand tube. A source of direct

current in series with the regulator operated a relay which, in turn,

actuated the solenoid ”E". Air was thus admitted to the system

through a capillary at "E", maintaining the pressure at the desired

level.

"F" was a 12 liter flask used as a ballast to minimize pressure

fluctuations. Vacuum was maintained by a continuously operating

mechanical pump.

The efficiency of the column was tested at atmospheric pressure

using benzene and carbon tetrachloride under total reflux. Thirty-

five theoretical plates were found. This probably bears little

relation to the number of theoretical plates under operating con­

ditions .

The first distillations were carried out at about ten milli­

meters pressure. The best fraction had a purity of 97 to This

best fraction was then redistilled and the best fraction from the

second distillation redistilled again. These latter distillations

were carried out at about two millimeters. The best fraction from

the third distillation was used without further purification. About

nine kilograms of methyl esters yielded about one kilogram of this

 16

final product.

The first separation was followed by observing the boiling

(24,25 ,26) (27^
temperatures and refractive index . These analytical

methods proved inadequate, however, for characterizing the samples

from the second and third distillations. The setting point was found

to be a more sensitive method. Setting points were measured in a

16 mm. test tube held inside a 25 mm. test tube which in turn irra.s

immersed in a water bath maintained at 2S.5°C. The smaller test

tube, containing about five milliliters of the liquid sample, was

placed into the larger tube after crystallization began. The

sample was stirred occasionally with a thermometer which remained

in the sample. The highest temperature reached was recorded as the

setting point. These values, although probably not a good indication

of the true temperature of transition, were nevertheless reproducible

to about 0.02* and served well in characterizing the product.

(3) Preparation of Palmitic Acid

Palmitic acid was prepared by saponification of the previously

purified methyl palmitate. 500 graiï's of methyl palmitate were re­

fluxed for about twelve hours with 850 ml. of water and 200 grams of

sodium hydroxide. After separating a little liquid the solid was

dried at 92®C. for four hours. The dried material was ground with a

glass mortar and pestle and placed, in 30 gram batches, into a Soxhlet

extractor. Extraction with diethyl ether proceeded for about six

hours. This process removed unsaponified material. Each batch was

heated with about its own weight of water and treated with 20;^ H 2S0,^
 17
until acid to litmus paper. The mixture vra,s boiled for several hours,

until the palmitic acid layer became clear. The aqueous layer was

decanted after cooling. The palmitic acid was melted and dissolved

in ether. The ether solution was then washed with ivater in a separatory

funnel. The solution was washed twice after the aqueous layer became

neutral to litmus paper. After drying with calcium chloride and

filtering, the ether was allowed to evaporate. Final drying was

accomplished under high vacuum. The palmitic acid was placed, in

about fifteen gram quantities, under high vacuum at 53 to 55°C.

Pumping was continued until the pressure fell to about 10” ^ mm. The

acid was then melted and placed for storage in a tightly closed

bo“tie. That portion of the acid which was used for preparing

sodium palmitate did not receive this final drying.

(4) Preparation of Omega. Sodium Palmitate

Ethyl alcohol was purified by refluxing with sodium hydroxide

and granulated aluminum followed by distillation, the first and last

portions of the distillate being discarded. A saturated aqueous

solution of sodium hydroxide was prepared, filtered through sintered

glass, and stored with the exclusion of 00%.

A three-necked flask was set up with a condenser protected

against CO2 by an ascarite tube. The center neck held a stirrer

with mercury trap. All stoppers were protected with metal foil.

About 50 grams of palmitic acid were accurately weighed into the

flask and dissolved in a mixture of 20 ml. of water and 200 ml. of

the previously purified ethanol. Into the third neck was placed a

pipette containing saturated sodium hydroxide, and protected by an

 18
ascarite tube. The pipette and alkali had previously been standardized

in such a vay that the resultant soap solution vrould contain a five

percent excess of palinitic acid. The sodium hydroxide was allowed

bo drop slowly into the refluxing acid solution. The resulting

solution vras boiled to remove the solvent, first at atmospheric,

then at reduced pressure. After this step no further precautions

were taken to exclude COg.

The dry product was ground and placed in small batches under

high vacuum (10 ^ mm.) and heated at 190°C for several hours. The

palmitic acid which distilled out wss cleaned off the tube and the

treatment was repeated until after several hours no further palmitic

acid appeared.

The sodium palmitate, upon cooling, was in the omega modifica­

tion. The product was protected against water vapor.

(5) Preparation of Delta Sodium Palmitate

Approxima.tely 90 grams of sodium palmitate vrere dissolved

in two and a half liters of distilled water. The solution was boiled,

filtered and allowed to cool. The water was removed by slow evapora­

tion with very moderate vrarming. The sample was protected from COg

during the process. Overheating during the evaporation was carefully

avoided since it might have led to the beta phase. Final dehydration

was accomplished by pumping under a good vacuum. It was discovered

later, however, that this pumping was not prolonged enough to dry the

sample completely. This point is discussed further below.

(6) Purity Determinations

The purity of the palmitic acid sample was determined by a

 19
(28}
method like that of Taylor and Rossini . Forty^eight grams

were placed in a 30 x 200 mm test tube which was supported inside a

larger tube. The space between the two tubes was partially evacuated.

The temperature outside the system was about 26*0. A platinum

resistance thermometer^ previously calibrated by the Bureau of

Standards, was immersed in the sample. The sample was stirred

mechanically viiile the resistance of the thermometer was measured

with a Mueller bridge. About an hour and a half were required for

complete solidification. Extrapolation of a portion of the curve

gave, for the freezing point of the sample, 62.63"C. The mole

fraction impurity was estimated from the equation

Nj = (Tf - Tz);

where ^ H^, the heat of fusion, was 13,120 cal.C^?); T^, the melting

point of the sample, was 335«S® K; and r was the fraction of the

sample solidified when the temperature had fallen to Tz. The value

of r was estimated from the time required for solidification. When

the sample was 59^ solidified the temperature had fallen 0,045 degrees

below T^. Substituting these values,

(0-045)

= 0.0018.

This gives an estimate of the impurity even though the assumption

that no solid solutions are formed is open to question. On the basis

of these results the freezing point of pure palmitic acid was calcu­

lated to be 62.68°C. This compares favorably with Francis and Pipers

setting point, 62.60*0., but is somewhat lower than the value given
 20

by Guy and Smith

(16), 62,75‘
, *C. The difference is probably to be

attributed to faulty thermometer calibration. The impurity probably

was predominantly stearic acid.

It was not found possible to determine directly the purity of

the methyl palmitate or sodium palmitate. The contamination by

stearate can safely be set equal to that found in the palmitic acid,

but the possibliity remains that other impurities may have been intro­

duced, Every effort was made to prevent this.

Cooling curves on methyl palmitate do not show typical behavior.

After initial supercooling the temperature continues to rise. In

the case of a relatively pure sample this increase persists until

the material has almost completely solidified. The setting point of

the sample was found to be 29.59®C, This may be compared with

Francis and Piper’s^^^^ setting point of 29*20®, their melting point

of 30.55®, and Guy and S m i t h c l e a r i n g point of 29.55°* An

attempt was made to determine the purity calorimetrically, but a

similar behavior was observed, Mien the temperature was plotted

versus the reciprocal of the fraction melted the data showed a marked

deviation from the expected straight line relationship. These

anomalies are probably to be attributed to the complicated phase

relationships in the vicinity of the melting point. In addition to

the estimated 0,2% methyl stearate, the sample may be contaminated

by traces of decomposition products.

Samples of sodium palmitate were tested for palmitic acid,

sodium hydroxide and carbonate, all with negative results within the

accuracy of the methods. It v/a.s assumed that, except for the

 21

presence of water, the purity of the sodium palmitate samples was

close to that of the palmitic acid used in their preparation.

Drying soap samples in the laboratory oven was found to be

an unsuitable method of water analysis. In order to drive off the

last traces of water a temperature of about 1$0*C is required. At

this temperature oxidation may take place, with resultant erroneous

values of water content. Water analyses for this research were made

by placing weighed samples under high vacuum (10~^ mm) at a temperature

of 105 to 110°C. Constant weight was achieved after about two hours.

In general, samples were maintained under these conditions for a

minimum of six hours.

Samples of the palmitic acid and sodium palmitate were sent to

the Proctor and Gamble laboratories where X-ray diffraction analyses

were made by Dr. F. B. Rosevear. The phase characterizations reported

below are those indicated by Dr. Rosevear.

 22
III EXPERDIENTAL PROCEDURE M D DATA

(l) Heat Capacity Determinations

The apparatus and procedures used in the Cryogenic Laboratory

of The Ohio State University have been adequately described both in

the generally available literature ( ^ ,33) ^ doctoral

dissertations^^^'.

Heat capacity, Cp, is defined as (<} H/ ^ T)p, where H is the

heat content, T, the temperature, and P, the pressure. In practice

a known amount of energy is added to the calorimeter and sample. The

resultant temperature change is measured, and the quotient,2^ H/ A T,

gives the average heat capacity.

Two methods are commonly used today for low temperature

calorimetry. In the adiabatic method the calorimeter is surrounded

by a shield that is maintained at the calorimeter temperature. It is

then assumed that no heat leaks to or from the calorimeter. In the

isothermal or N e m s t method the calorimeter is surrounded by a massive

cylinder maintained at a nearly constant temperature during the

energy input. One person may obtain the data by the isothermal method.

The adiabatic method requires a second operator to maintain the shield

at the calorimeter temperature, but the calculations in this case are

somewhat less tedious. For low temperature work both methods are

capable of about the same accuracy. At temperatures above 300"K the

radiation corrections became so lar^e that the isothermal method is

no longer suitable for accurate work. For the same reason the

adiabatic method becomes more difficult, and both methods have

usually been discarded in favor of the use of the ice calorimeter for
 23
high temperature work. The isothermal method has been selected

for low temperature calorimetry in the Cryogenic Laboratory of

The Ohio State University.

The heat leak was minimized by reducing the pressure to less

than 10""5 mm. The whole assembly was immersed in a Dewar flask

which held liquid air or liquid hydrogen coolant.

The copper calorimeter was wound with a gold wire used as a

thermometer - heater. The resistance was measured by observing

simultaneously the potential across the thermometer and across a

standard resistor in series with the thermometer as a very small

current was passed through the circuit. Temperatures so measured

were corrected by continuous comparison with a calibrated thermo­

couple soldered to the calorimeter. Correction was also made for

the effect of the surroundings on the temperature measured by the

resistance thermometer. The measured A T was corrected for loss and

gain of heat to and from the surroundings.

During energy input the current and potential were measured in

a similar manner except that a voltage divider was used to bring the

measurements within the range of the instrument. Corrections were

made for the resistance of lead wires and for heat dissipated in the

voltage divider resistance which was in parallel with the heater.

Heat capacities calculated from these measurements were corrected

for the heat capacity of the calorimeter and the helitun which filled

the void space inside the calorimeter.

The heat capacity of the empty calorimeter has been reported

(13)
by Wood . The data are repeated in Table 1. Table 2 gives the
 24

Table 1

Heat Capacity of Empty Calorimeter

Weight: 85.O6S 5 grams

Run Mean Temperature Heat

Temperature Increment Capacity

Deg. K, Deg. K, Gal/deg

II 15.33 3.162 .1271

II 18.38 2.284 .1845
II 21.53 2.156 .2719
II 23.87 1.680 .3535
II 25.53 1.427 .4201
II 27.68 2.718 .5231
II 30.72 3.723 .6874
II 33.87 3.395 .8841
II 37.32 4.288 1.112
II 41.27 4.120 1.386
II 45.56 3.983 1.699
II 58.36 3.420 2.647
II 62.52 4.344 2.921
II 68.13 6.497 3.270
II 75.44 7.946 3.704
I 77.63 6.375 3.808
II 82.87 6.978 4.103
I 83.64 5.913 4.150
I 88.99 6.170 4.420
I 95.71 7.340 4.676
I 103.44 7.889 5.042
I 110.88 7.134 5.258
I 121.58 7.643 5.557
I 129.52 8.257 5.759
I 138.53 9.805 5.955
I 147.71 9.201 6.132
I. 161.84 8.179 6.369
I 175.15 7.395 6.570
I 188.16 7.362 6.702
I 200.30 6.298 6.838
I 210.25 5.496 6,869
II 211.59 5.836 6.896
I 219.61 4.297 6.929
II 222.27 5.526 6.957
 25

Table 1 - continued

Heat Capacity of Empty Calorimeter

Weight: 85.0685 grams

Run Mean Temperature Heat

Temperature Increment Capacity

Deg, K, Deg. K. Gal/deg

I 230.30 4.022 7.079

I 241.91 3.786 7.173
II 243.30 4.149 7.097
II 252.08 4.782 7.149
I 253.33 3.592 7.254
I 262.93 3.464 7.260
II 270.21 4.380 7.299
I 271.93 3.357 7.246
I 280.67 2.967 7.331
II 286.93 3.055 7.403
I 289.04 2.826 7.459
II 292.98 2.964 7.465
II 295.66 2.946 7.440
I 297.13 2.712 7.537
II 299.00 2.917 7.416
II 302.66 2.853 7.484
I 305.14 2.652 7.452
II 305.14 2.861 7.390
 26

Table 2

Heat Capacity of Empty Calorimeter

Weight : 85 .324 grams.

Run Mean Temperature Heat

Temperature Increment Capacity

Deg. K, Deg. K. Cal/deg

III 62.26 8.642 2.902

III 79.28 5.254 3.926
III 95.05 6.719 4.678
III 109.94 5.301 5.221
III 122.05 7.100 5.556
III 138.43 5.969 5.933
III 157.01 5.052 6.286
III 168.51 6.636 6.457
III 183.31 6.004 6.627
III 199.37 7.421 6.792
III 214.30 6.802 6.914
III 229.53 6.290 6.992
III 243.96 5.806 7.150
III 259.18 5.383 7.256
III 272.34 3.689 7.407
III 282.52 3.556 7.373
III 285.75 3.526 7.411
III 292.46 3.740 7.435
III 296.19 3.695 7.442
III 299.58 3.656 7.429
 27

results of a subsequent run made after the calorimeter had been

revround. These data agree within experimental error with the original

calibration.

Measurements were made in terms of International Volts and Ohms.

Electrical energy was converted to thermal units by dividing by 4.1833.

Results were thus obtained in terms of the defined calorie. All

weights were reduced to vacuum.

From the smooth curves drawn through the data the thermodynamic

functions heat content, H® - H§; entropy, S“; and the free energy

function, - lE— ZSal^ were calculated.

(2) Methyl Palmitate

A sample of methyl palmitate was melted and poured into the

calorimeter, very nearly filling it. Ten days after the sample had

solidified in the calorimeter run I was made, covering the range 72 to

286“K. Twenty-six days later run II was made covering the liquid

hydrogen range. Ten days later (run III) the measurements were

extended to the melting point and the data for fusion rijn A were taken.

Fusion run B and two heat capacity determinations on the liquid

(Run IV) were made after five days. The sample was then removed from

the calorimeter. The purity of the sample was estimated to be about

99.79G.

Two years later it seemed advisable to make further determina­

tions in the vicinity of the melting point. The calorimeter was filled

with another sample. Seven days after solidification run V and

fusion run C were made. Run IfE, including fusion run D, was made

about one and a half days after solidification. Finally the data for
 28

run VII were taken over a three hour period beginning two hours after
solidification. After finishing these determination it was discovered

that 1,1% of the sample had leaked from the calorimeter and distilled

to the surrounding cylinder. Since it is not known when this loss

occurred, it must be supposed that each of the results of runs V,

VI and VII was from 0 to 1.1% too low. A considerable amount of pre­

melt iig occurred in these later runs, although none had been observed

previously. A setting point determination gave 29.50°C. This

indicated that the material had been contaminated. The cause of the

contamination is not known. The purity of this material was estimated

to be 97%.

The results of the calculations are shown in Table 3, and are

plotted in Fig. 3. The extrapolation to 0°K was carried out on the

C'n " '
function-^ . In calculating the heat of fusion it was necessary

to know the temperature of the solid-liquid transition. Inasmuch as

neither the literature nor this research has yielded a reliable value,

the arbitrary value of 303.00"K (29.84"C.) was selected. Table 1+

shows heat capacities from a smooth curve, as well as derived

thermodynamic functions,

(3) Palmitic Acid

The sample investigated here was obtained by crystallization

from the melt. X-ray analysis confirmed the expectation that it

would be found to be phase "C". The air remaining in the calorimeter

after filling vdth the sample was replaced with helium. On the basis

of the cooling curve described above, the purity was estimated to be

99.8%.
 29

Results are shoivn in Table 5j with the results previously

reported by Parks and K e l l e y ^ a n d by Ward and Singleton^ . These

values are plotted in Fig. 4» Values taken from the smooth curve are

shovm in Table 6, with derived thermodynamic functions.

(4) Omega Sodium Palmitate

X-ray analysis showed the sample to be of the omega modification,

both before and after the heat capacity determination. Water analysis

as described above showed 0,08^ water before, and 0.14% water after

the run. On the basis of these results the sample can be said to be

anhydrous within the limits of experimental error. After filling the

calorimeter with the sample, the air was replaced by helium. Results

of the determination are shown in Table 7. Table 8 gives values read

from the smooth curve as well as derived thermodynamic functions. The

results are plotted, with those of the delta determination, in Fig. 5.

The extrapolation to zero degrees was accomplished by comparison with

(13)
the data of Wood for anhydrous beta sodium palmitate. From 60 to

150°K. the omega and beta curves differ at all points by less than one

percent.

(5) Delta Sodium Palmitate

A sample taken from the calorimeter was examined by Dr. Rosevear

by means of X-ray diffraction. He reported the sample to be delta,

A perfectly dry sample showed a slightly modified pattern. A water

analysis of sample from the calorimeter showed a water content of

0,79%. Results are shown in Table 9. A smooth curve was drawn

through the points and thermodynamic functions from this curve are

shoim in Table 10. The extrapolation to zero degrees was carried out
 30

in the same manner as in the omega calculation. The results of

Tables 9 and 10 are expressed in calories per mole of sodium

palmitate. That is, these are the values of the functions for one

mole of sodium palmitate and the 0.799^ water also present. To obtain

the thermodynamic functions for anhydrous delta, the heat capacity of

ice was subtracted. Values for ice were taken from the determination
(
of Glauque and Stout and from the extrapolation of their curve

from 273 to 300®K, The results are shown in Table 11. The original

points and the calculated curve for the anhydrous compound are shown,

with the omega results, in Fig. 5.

 31

Table 3
Heat Capacity of Methyl Palmitate
Weight of sample: Runs I through IV: 59.822 grams

Runs V through VII: 57.314 grams

Run Mean Temperature Heat

Temperature Increment Capacity

Deg. K, Deg. K. Cal/deg mol

II 13.80 0.961 2.76

II 15.49 1.317 3.30
II 18.32 2.999 4.64
II 21.30 2.212 6.26
II 23.53 1.824 7.54
II 25.61 2.138 8.77
II 27.98 2.534 10.18
II 30.99 3.490 12.17
II 34.15 3.836 14.29
II 37.15 3.194 16.32
II 40.52 3.563 18.32
II 44.47 4.363 20.80
II 48.88 4.495 23.50
II 53.54 4.887 26.41
II 59.75 5.773 30.08
II 65.72 5.921 32.85
I 66.67 7.885 33.31
I 74.54 7.725 37.43
I 82.83 8.813 41.17
I 91.60 8.733 44.64
II 100.50 8.949 47.58
I 101.27 10.676 47.96
II 107.90 8.027 50.04
I 111.95 10.814 54.80
II 115.51 7.227 52.47
I , 122.55 10.825 54.72
I 133.31 10.824 57.76
I 144.05 10.756 60.68
I 151.86 13.910 62.58
I 164.91 12.337 66.26
I 176.37 11.231 69.12
I 186.77 9.528 71.94
I 196.27 9.578 74.63
I 205.27 10.342 77.29
I 215.17 9.627 79.97
I 224.46 9.005 82.91
I 233.67 9.047 86.44
I 244.82 8.473 88.86
I 253.56 10.837 93.12
 32
Table 3 - continued
Heat Capacity of Methyl Palmitate
Weight of sample: Runs I through IV: 59.022 grams

Runs V through VII: 57.314 grams

Run Mean Temperature Heat

Temperature Increment Capacity

Deg. K. Deg. K. Cal/deg mol

I 263.29 9.311 97.39

I 272.56 9.404 102.01
III 280.36 4.857 104.54
I 281.31 10.223 105.79
VI 285.64 4.743 106.93
III 285.86 5.822 107.26
VII 285.96 4.665 108.44
VI 290.22 4.580 109.51
VII 290.66 4.490 111.22
III 291.34 5.573 110.58
VI 293.38 4.486 110.59
VII 295.01 4.259 116.60
III 296,66 5.380 112.86
VI 297.79 4.091 121.90
V 298.78 1.513 120.65
VI 303.47 2.223 139.6
IV 304.59 2.583 138.2
VI 305.59 1.861 136.4
IV 307.01 2.572 137.4
VI 307.39 1.868 134.4

Heat of Fusion at 303.00 deg. K.

ftun H
Kcal / mol

A 14.12
B 13.86
D 13.89
D 13.66
 33

Table 4

Thermodynamic Functions for Methyl Palmitate

T S S® H® - H8 T

Deg.K. Cal/deg mol Cal/deg mol Cal/mol Cal/deg me

20 5.49 2.91 38.2 1.00

40 17.99 10.46 270.5 3.70
60 30.09 20.11 754.2 7.54
80 39.92 30.16 1457.8 11.94
100 47.56 39.91 2334.6 16.56
120 53.96 49.14 3349.9 21.22
140 59.59 57.88 4485.7 25.84
160 64.93 66.18 5729.4 30.37
180 70.14 74.12 7080.1 34.79
200 75.66 81.80 8537.4 39.11
220 81.74 89.29 10110 43.33
240 88.26 96.67 11809 47.47
260 96.05 104.04 13650 51.54
280 104.88 111.47 15658 55.55
300 114.27 119.03 17849 59.53
 HEAT CAPACITY OF
METHYL RXLMITATE

-o

0) fOO
o
E
n $
S'
T3

^ S
o
o o-
o
50 Run Symbol

IV 6
V a
VI 9
V I -o

100 200 300 ^

Temperature, °K
 35
Table 5
Heat Capacity of Palmitic Acid
Weight of Sample: 43.282 grams

Run Mean Temperature Heat

Tenqjerature Increment Capacity

Deg. K. Deg. K. Cal/deg mol

IV 14.91 1.405 1.94

IV 16.59 1.034 2.68
IV 18.59 1.676 3.36
IV 21.32 2.037 4.56
IV 24.51 2.702 6.43
IV 28.03 3.990 8.62
IV 32.09 4.275 11.15
IV 36.60 5.010 14.04
IV 41.86 5.524 17.39
IV 47.37 5.741 20.72
IV 52.92 5.616 24.00
IV 58.94 6.642 27.68
II 59.38 6.103 28.12
I 60.18 3.974 28.49
III 64.27 3.118 30.26
I 64.78 5.224 30.24
II 64.98 5.183 30.18
IV 65.57 5.525 31.13
III 68.84 5.585 32.19
I 69.67 4.595 31.89
III 74.38 5.623 34.71
I 74.58 3.995 34.66
II 74.83 3.936 34.75
I 78.98 4.694 36.94
II 79.52 5.464 36.99
III 81.58 7.485 37.60
I 83-83 5.033 38.65
II 84.71 4.887 39.02
III 89.04 7.549 40.23
II 89.39 4.470 40.54
II 94.56 5.886 42.00
III 95.99 6.795 42.53
II 99.62 5.423 43.79
II 101.80 5.237 44.24
III 102.42 6.106 44.44
II 106.82 4.859 45.67
III 108.88 7.219 46.53
II 112.28 6.115 47.42
III 116.69 8.234 48.76
II 117.79 5.684 48.86
II 124.18 6.869 50.43
 36

Table 5 - continued

Heat Capacity of Palmitic Acid

Weight of Sample: 43.2S2 grains

Run Mean Temperature Heat

Temperature Increment Capacity

Deg. K. Deg. K. Cal/deg mol

II 130.84 6.352 52.28

II 136.99 5.948 53.77
II 137.71 5.869 54.04
II 144.14 6.943 55.78
II 150.65 6.496 57.67
II 164.99 7.028 61.26
II 172.22 8.018 62.66
II 179.98 7.525 64.71
II 187.98 8.395 66.95
II 196.09 7.894 68,94
II 196.22 7.884 69.16
II 204.55 8.667 71.69
II 213.00 8.136 74.10
II 221.74 8.887 76.34
II 230.32 8.346 79.10
II 239.12 7.831 82.08
II 247.22 8.478 84.87
V 250.46 7.525 85.41
II 254.62 8.088 87.67
II 255.16 8.027 87.71
V 257.84 8.002 88.86
II 263.08 8.600 91.53
VII 264.14 6.900 91.78
VI 264.22 7.638 91.76
VII 271.46 7.435 95.74
II 271.69 8.064 95.62
VII 277.64 7.116 98.52
II 280.19 8.480 100.97
VII 283.01 6.830 101.12
II 287.47 8.123 103.77
VII 289.41 6.520 104.51
II 295.56 7.639 108.62
VII 295.80 6.210 108.40
VII 301.60 5.941 111.89
II 302.12 5.651 113.12
II 157.71 7.490 59.59
 37
Table 5 - continued

Heat Capacity of Palmitic Acid

Weight of Sample : 43.282 grams

Results of Parks Results of Ward

and Kelley 10,19 and Singleton 17
Heat Heat
Temperature Capacity Temperature Capacity

Deg. K* Cal/deg mol Deg. K. Cal/deg

88.4 41.0 200 74.1

93.7 42.8 250 90.3
97.4 43.8 280 101.5
102.3 45.4
107.1 46.7
110.2 47.7
111.7 47.7
151.9 58.7
160.8 60.8
193.5 69*5
197.6 70.5
215.4 75.6
234.5 82.0
237.9 83.1
274.9 98.2
275.3 98.5
289.4 106.9
292,5 110.5
 38
Table 6

Thermodynamic Functions for Palmitic Acid

- (F° - Hg)
T S* - H8 T
Cp
Deg.K. Cal/deg mol Cal/deg mol Cal/mol Cal/deg mol

20 4.00 1.69 23.6 0.51

40 16.19 8.04 221.2 2.51
60 27.97 16.89 665.6 5.80
80 36.96 26.24 1319.8 9.74
100 43.72 35.24 2129.1 13.95
120 49.39 43.73 3062.0 18.11
140 54.68 51.74 4102.3 22.44
160 59.81 59.38 5247.9 26.58
ISO 64.82 66.71 6493.6 30.63
200 70.27 73.82 7843.7 34.60
220 75.91 80.78 9305 38.48
240 82.27 87.64 IO 885 42.29
260 89.96 94.52 12604 46.04
280 99.78 101.54 14499 49.76
300 111.28 108.80 16604 53.45
 HEAT CAPACITY OF
PALMITIC ACID

100

0)
o
E
0)
2
-Si S’
"O

- F .2
k.
50

o
O
o This research
• Porks and Kelley
t>Ward and Singleton

100 200 300

Temperature, ®K
 40

Table 7

Heat Capacity of Omega Sodium Palmitate

Weight of Sample: 33.009 grams

Run Mean Temperature Heat

Temperature Increment Capacity

Deg. K, Deg. K. Cal/deg mol

IV 58.37 4.515 27.15

IV 64.01 6.659 30.00
I 65.77 5.522 30.35
IV 69.52 4.691 32.44
I 72.13 7.167 33.97
I 77.32 6.864 36,66
I 84.50 7.530 39.74
I 88.67 6.966 41.15
I 95.21 6.150 43.98
I 97.50 5.999 44.76
I 104.18 7.345 47.12
I 110.84 6.675 49.26
I 118.30 7.841 51.98
I 125.60 7.159 54.08
I 133.27 8.242 56.32
I 141.54 7.542 58.64
I 149.60 8.678 60.79
I 157.62 8.024 63.37
I 158.74 8.052 63.29
I 166.58 7.500 65.63
I 174.71 8.473 67.55
I 182.04 7.977 69.62
I 190.37 8.808 72.16
I 198.80 8.413 74.54
I 206.82 7.926 77.18
I 214.57 8.790 79.40
I 223.58 8.250 82.28
II 224.68 8.433 82.25
II 232.67 8.079 84.44
II 240.22 7.681 87.54
II 247.82 7.308 91.00
III 250.10 7.187 91.43
III 256.82 6.853 94.46
III 263.16 6.575 97.73
III 269.73 6.294 101.58
III 276.11 5.997 105.95
III 281.15 5.828 107.86
III 286.90 5.571 112.35
III 292.43 5.399 114.82
III 297.44 5.233 117.61
 41
Table 8

Thermodynamic Functions for Omega Sodium Palmitate

- - Hg)
T S“ H“ - H8 T

Deg, K Cal/deg mol Cal/deg mol Cal/mol Cal/deg me

20 4.60 2.07 29.2 0.61

40 15.76 8.42 225.0 2.80
60 27.80 17.14 663.1 6.09
80 37.82 26.57 1323.5 10.03
100 45.67 35.88 2161.3 14.27
120 52.41 44.82 3143.6 18.62
140 58.20 53.34 4250.8 22.98
160 63.68 61.47 5469.9 27.28
180 69.13 69.29 6798.1 31.52
200 74.94 76.87 8238.0 35.68
220 80.89 84.29 9796 39.76
240 87.51 91.60 11478 43.78
260 96.12 98.93 13310 47.74
280 107.46 106.46 15343 51.66
300 119.59 114.28 17612 55.57
 42
Table 9

Heat Cftpacity of Delta Sodium Palmitate

Weight of Sample: 39.934 grams Sodium Palmitate, 0.318 grams

Run Mean Temperature Heat

Temperature Increment Capacity

Deg. K. Deg. K. Cal/deg mol

I 58.25 4.031 27.73

I 64.25 5.635 30.61
I 70.94 7.680 34.14
I 78.51 7.516 37.89
I 85.96 7.467 41.16
I 93.81 8.574 44.04
I 100.52 9.383 46.62
I 111.01 11.755 50.18
I 122.15 10.776 53.55
I 132.12 10.291 56.54
I 142.37 10.238 59.25
I 152.04 9.971 62.02
I 162.03 9.988 64.52
I 171.06 9.926 66.50
I 180.81 10.074 68.48
I 190.95 10.441 71.37
II 201.05 10.441 74.50
II 210.95 9.748 77.13
II 220.51 9.756 79.90
II 230.56 10.228 82.92
II 238.26 10.258 85.69
II 248.95 9.635 88.73
II 256.96 9.247 91.19
II 266.01 8.700 94.67
II • 274.75 8.647 98.50
II 282.02 8.284 100.52
II 290.40 8.291 104.22
II 298.21 7.516 107.42
 43

Table 10

Thermodynamic Functions for Delta Sodium Palmitate

•with 0,79% VJater
- (F° - Hg)_.
T Gp S' H' - Hg T

Deg. K Cal/deg mol Cal/deg mol Cal/mol Cal/deg mol

20 4.68 2.10 29.7 0.62

40 16.02 8.56 228.9 2.84
60 28.25 17.42 674.0 6.19
80 38.57 27.03 1346.8 10.19
100 46.30 36.49 2198.2 14.51
120 53.10 45.54 3193.6 18.93
140 58.77 54.16 4313.2 23.36
160 64.06 62.36 5542.8 27.72
180 68.61 70.17 6869.1 32.01
200 73.90 77.66 8292.7 36.20
220 79.82 84.99 9830 40.30
240 85.96 92.19 11487 44.33
260 92.53 99.32 13270 48.28
280 99.99 106.44 15194 52.18
300 108.44 113.63 17276 56.04

Table 11

Thermodynamic Functions for Anhydrous Delta Sodium Palmitate

- (F' - H^)
T S' H' - H8 T
Cp
Deg. K Cal/deg mol Cal/deg mol Cal/mol Cal/deg mol
20 4.62 2.08 29.4 0.61
40 15.85 8.46 226.2 2.81
60 27.98 17.23 666.6 6.12
80 38.18 26.74 1332.8 10.08
100 45.83 36.11 2175.3 14.36
120 52.54 45.07 3160.6 18.73
140 58.13 53.60 4268.0 23.11
160 63.33 61.71 5484.1 27.43
180 67.81 69.42 6795.3 31.67
200 73.04 76.83 8202.2 35.82
220 78.88 84.06 9721 39.87
240 84.96 91.18 11358 43.86
260 91.48 98.23 13121 47.77
280 98.84 105.27 15022 51.62
300 107.21 112.37 I7O8I 55.43
 HEAT CAPACITY OF
SODIUM PALMITATE

100

■ z 50

o Omega (anhydrous)
• Delta (0.79% water)
— Delta (anhydrous)

100 200 300

Temperature “K
 45
IV DISCUSSION OF HEAT CAPACITY DATA

(l) Accuracy

Bower^^^^ has discussed the errors inherent in the apparatus and

procedures used. His estimates of the probable error from 45“ to 300‘^K

was 0.2%, increasing to about 1% at 20“K, and to as high as 5% at 13“K.

This research did not achieve such a degree of accuracy. A discussion

of the precision of the results will be found below.

The errors ma.y be considered as "consistent" vdien they affected

all results in the same way, and "variable" when they affected the

individual determinations in a random fashion. The most significant

consistent errors were the calibration of the thermocouple, the weight

of the sample and of the calorimeter, the calibration of the electrical

components, especially the standard resistors and voltage divider, and

impurities in the sample. With the exception of the last named, these

probably contributed no more than 0,1% to the error. In the case of

the sodium palmitate the uncertainty in the water content may have

contributed another 0,1%. These errors contributed additively to the

calculation of the thermodynamic functions, so that the limit of

accuracy can be set at about 0.1 to 0.2%.

Variable errors, including most significantly the uncertainties

in determining the temperature change and the corrections for heat

leak, were reflected in the scatter of the results. The precision

was estimated by noting, at each temperature, the difference, d,

between the observed result and the smooth curve. The standard

deviation of the heat capacity results v/as defined.

 46

SC
=(1Z
' n-1

where n was the number of observations. The heat content and entropy

may be considered to be approximately equal to the summation of CpZ^ T

and (Cp/T)2^ T respectively over all temperature intervals, each interval

including an experimental heat capacity determination. To estimate

the precision of the heat content and entropy results therefore, the

temperature scale was divided into a series of intervals. /\ T, each

including one of the experimental points. The quantities S ~ d/^ T

and ^ / T were calculated and the standard deviations were defined.

and
8g =f§T/T)^.
Results of a similar procedure for the empty calorimeter were

included in the calculations. Table 12 shows the results, including

(in parentheses) the corresponding percentages. Deviations for Wood's

beta determination are included for that portion df the curve used in

the extrapolation of delta and omega. These values can be considered

estimates of the error except that the error in (K" - H§) was probably

about 0,2fo,

The standard deviation of the heat of fusion results for methyl

palmitate was 0,19 Kcal. This is equivalent to 1.4%*

(2) Methyl Palmitate

The apparatus used was not suitable for measurements above room

temperature. The resistance thermometer was subject to strain, making

 Table 12

Standard Deviations

SC "H =S
Cal/deg mol Cal/mol Cal/deg mol

T, “K 0-40" 40-80* 80-200* 200-300* 300* 300*

MeP 0.03(1,%&) 0.15(.5#) 0.12(.2#) 0.5K.6#) 16(.09#) 0.31(.3#)

HP 0.07(2#) 0.33(1.2#) 0.11(.2#) 0.33(.4#) 9(.05#) 0.16(.14#)

S NaP 0.21(.4#) 0.37(.4#) 14(.09#) 0.35(.3#)

0J> NaP 0.26(.4#) 0.47(.5#) 15(.09#) 0.36(.3#)

/3 NaP 0.24(5#) 0.58(2#)

 48
measurements unreliable. Heat leaks were high because of the increased

radiation at higher temperatures. For the same reason it was difficult

to control the temperature of the surroundings, especially during the

fusion runs. In addition, the loss of sample made runs V, VI and VII

and fusion runs C and D very unreliable. Because of these considerations

the results on the heat of fusion and the heat capacity of the liquid

must be considered approximate.

An error evidently was made in observing or calculating the

data for the point at 112®. Repeat determinations showed no evidence

of an anomaly.

The heat capacity curve of the liquid is not well defined. How­

ever the downward trend ir nc doubt real. This may be an indication

that some order remains in the liquid just above the melting point and

that this crdsr decreases ra%idly as the temperature is raised.

There remains some doubt concerning the phase of methyl palmitate

present in the calorimeter during runs I, II and III, However, since

the results were consistent,, it appears that whatever phase changes

occur during the period between ten and forty-six days after solidifying

do not markedly effect the heat capacity.

(3) Palmitic Acid

Some difficulty was encountered in drawing the curve through

the points in the region 140 to 180®K, Several points lie slightly

above the smooth curve, which might indicate a very small anomaly.

The maximum heat effect involved here is about 12.5 cal./mole. It

seemed much more likely, however, that this irregularity is to be

 49

ascribed to experimental error, and the best smooth curve was drawn
through the points.

Heat capacity determinations are in general expected to show

S-shaped curves leveling off at higher temperatures. The heat capacity

curve of palmitic acid shows an upward inflection at about 170"K, as

do the curves of methyl palmitate and sodium palmitate. This is very

probably due to a beginning of libration in the molecules. Although

no precise determinations have been madé above room temperature, it

seems likely that this trend continues to the melting point.

(4 ) Sodium Palmitate

The heat capacities of delta and omega sodium palmitate do not

differ greatly below 1$0*K. The difference then increases until at

room temperature the heat capacity of delta is ten percent lower than

that of omega.
 50

V ENTROPY DIFFERENCES AND STRUCTURE

(1) Crystal Structure

A great deal of work has been done on these compounds with

X-ray diffraction techniques. Very little of this -work has been

directed toward an elucidation of the crystal structure. The purpose

has been to make comparisons among the various members of the several

homologous series, and among the polymorphic forms in which they exist.

X-ray diffraction has been widely used as a method of analysis.

In general, these compounds form monoclinic crystals, made up

of double layers of molecules with the carboxyl groups in juxtaposition.

Almost all of the work kas been confined to the powder method of X-ray

analysis.

The crystal spacings for methyl palmitate have been reported by

Shearer^^^) as follows: d^ = 22,OA, d^ = 4*0?A, da = 3.72A, Francis

and Piper^^^^ give only the long spacing, 43,45 A. Shearer’s value for

di corresponds to the distance between planes separated by one molecule,

Francis and Piper’s value is for the distance between planes of polar

groups.

Millier^ ' reported these results for the spacings of palmitic

acid: d; = 34,?A, dg = 4.OSA, da = 3 .65A, Francis and Piper^^^^ gave

the single value, 35»6A. These results are for the form obtained by

crystallization from the melt, which was the form used in the heat

capacity work. Comparison with the spacings of methyl palmitate shows

an agreement in the side spacings, indicating a similarity in lateral

configuration. Comparisons between the long spacings do not show

 51

differences in chain length, however, since the long spacings are

affected also by the angle of tilt.

Determinations of the crystal structure of anhydrous sodium

palmitate phases has been limited to X-ray diffraction studies of

powder samples, since it has not been found possible to prepare single

crystals large enough for rotating crystal studies. Ferguson, Rosevaar

and Stillman' ^ have listed values of d/n for these and other phases.

The strongest lines appear in the case of the omega sample at 4.03 and

4.6SA, tdiile for the delta the lines indicate distances of 3.85 and

4.55A. This information does not make it possible to determine the

symetry of the crystals or the dimensions of the unit cells. Neither

does it indicate whether or not the crystals are perfectly ordered.

It does indicate, however, that the difference between these two forms

cannot be accounted for on the basis of disorder effects alone. The

effect of disorder is to broaden the lines of the po-vjder photograph.

Other factors may contribute to this broadening, however, so that a

diffuse pattern does not necessarily indicate crystal imperfections.

(2) Entropy Differences

From the tabulations of entropy in Tables 4j 6, 8 and 11 the

differences in entropy between the several compounds may be found. These

are given in Table 13.

The third law of thermodynamics states that the entropy of every

pure substance becomes zero at 0®K provided that it exists as a per­

fectly ordered crystal at 0“K. From the data at hand it cannot be stated

with certainty that there is no disorder in the sodium palmitate samples.

 52

Table 13

Entropy Differences in Cal/deg mol

T,deg K 60 NaP - ^ NaP MeP - HP S NaP - HP

20 -.01 1.22 .39

40 -.04 2.42 .42
60 -.09 3.22 .34
80 -.17 3.92 .50
100 -.23 4.67 .87
120 -.25 5.41 1.34
140 -.26 6.14 1.86
160 -,24 6.80 2.33
180 -.13 7.41 2.71
200 .04 7.98 3.01
220 .23 8.51 3.28
240 .42 9.03 3.54
260 .70 9.52 3.71
280 1.19 9.93 3.73
300 1.91 10.23 3.57
 53
It has been pointed out in the previous section, however, that
the entropy difference between these two samples cannot be ascribed

to disorder alone. The two forms are distinct crystalline modifica­

tions, and the relatively small entropy difference may be ascribed to

a difference in the vibrational entropies associated with the two

crystal lattices.

The lower members of the fatty acid series are knovm to form

hydrogen bonds. It seems probable that hydrogen bonding occurs also

in palmitic acid. Many configurations of the carboxyl groups might

be postulated. Crystal structure data do not yield much information

on this point. It may be that two molecules dimerize through the

formation of two hydrogen bonds. If this is the case there are two

possible positions for each dimer, one in which it has the same

hydrogen bond configuration as its neighbor and one in which it is its

mirror image. It seems likely that such disorder would persist to

the lowesttemperatures and would therefore contribute, if the distri­

bution is random, R In 2 to the entropy of a mole of dimer. This

vrould then represent an entropy of 1/2 R In 2 = 0.69 cal/deg per mole

of palmitic acid in addition to the entropy found experimentally.

Another possibility is that every carboxyl group may be hydrogen

bonded to each of two opposing molecules, thereby forming a chain of

oxirgen atoms joined together by hydrogen bonds. Such a structure

could have but two configurations for each long chain of carboxyl

groups, ■vdiich would contribute negligibly to the disorder entropy.

The formation of hydrogen bonds restricts the vibration of the

atoms involved. This results in a lower entropy than would be found

 54
if the hydrogen bonds were not formed. The entropy difference

between methyl pa,lmitate and palmitic acid is seen to be about ten

calories per degree per mole. Th^r is due in part to the added

degrees of freedom resulting from the replacement of hydrogen by a

methyl group, but may also be partly attributable to the reduction

of the vibrational entropy of the palmitic acid crystal by the

formation of hydrogen bonds.

In an effort to separate these two factors a rough estimate

will be made of the entropy difference between a methyl ester and

the corresponding acid. It will be assumed for simplicity that all

vibration frequencies in the two molecules are identical except those

directly involving the H atom in the acid, or the CH3 group in the

ester. The carboxyl group is apparently planar, and the vibrational

modes associated with the acidic H atom and their estimated frequencies

are as follows:

Stretching of OH bond - - --- - - - - - - - - 3570 cm“^

In-plane COH angle bending --1340

Out-of-plane bending or torsion - - - - - - - - 230

The OH stretching frequency is that observed in formic acid, HCOOH^^*^^

The in-plane bending of the acidic H in formic acid is not assigned

by Herzberg^^^\ It seems likely that the 1206 cm""^ infrared bond

of formic acid is the in-plane bending of the aliphatic H, since the

similar mode-r) 5 in formaldehyde, HgCO, has been assigned a frequency

of 1280 cm"*^ (39^ There is no other observed bond for formic acid

which can reasonably be assigned to in-plane bending of the acidic H.

The OOH angle bendings in hydrogen peroxide, HOOH, have been assigned
 55
at I/4OO cm“^ (reference 39, page 301), and the COH angle bending
«— T —"1
in methyl alcohol, GH3OH, at 1370 cm in the Raman and 1340 cm

in the infrared (reference 39, page 335). The 1340 cm ^ value is

confirmed by the isotopic shift of the corresponding infrared bond

in CH3OD, and ■
'
aÔ.II be adopted for the in—plane bending in the present

case. The^ 2 cm ^ Raman line observed for formic acid can scarcely

be assigned to anything except the torsional mode. This is supported

by the occurrence of a 270 cm ^ infrared bond in methyl alcohol which

must be the corresponding torsional mode in that molecule.

The entropy contributions of these three vibrations in the

harmonic oscillator approximation at 300®K are:

Stretching 0.00

Bending 0.02

Torsion 1.89

Total 1.91 cal/deg mole

The out-of-plane bending or torsional mode may also be re-

^ r d e d as an internal rotation. The similar problem of the barrier

to internal rotation in methyl alcohol has been the subject of many

investigations, H a l f o r d ^ h a s given a review of recent vrork on this

problem. Apparently it is now established on the basis of micro­

wave data that the barrier is 932 cal/mole (326 cra”^), a value which

is much lower than previous estimates based on thermodynamic data.

This low barrier would indicate that the harmonic oscillator

calculation of the torsional entropy will not be reliable. Halford

has estimated the internal rotational contribution in methyl alcohol

as 1.4 entropy units at 300“K, a value in reasonably good agreement

 56
with the value calculated above for f o m i c acid.

The vibrational modes associated with the CH 3 group in a methyl

ester, may be divided into those involving primarily motion of the H

atoms with respect to the carbon atom, and those involving motion

of the entire CH3 group (including the C atom). The frequencies of

the first type are sufficiently high so that they do not make much

contribution to the entropy, and the following approximate estimates

are therefore adequate:

CH stretching (3) 2950 cm~^

CH bending (1) 1380

CH bending (2) I46O

CH3 rocking (2) II 50

The value of the CH3 rocking frequency is most variable. The value

of 1150 cm“^ is based on the rocking frequencies observed in methyl

alcohvl and dimethyl ether, (CH3)20 (reference 39, page 334), since

in these molecules the methyl group is bonded to an oxj’-gen atom

as in an ester.

The modes of vibration involving motion of the entire methyl

group, and their estimated frequencies are as follov.^s:

Stretching of 00 bond - - - - - - 1000 cm"^

In-plane COG angle bonding -- - - - - - - - - - - 400

Out-of-plane bending or torsion - - - - - - - - - SO

The 00 bond stretching is approximately the average of the symmetric

and unsymmetric stretchings of the COG skeleton in dimethyl ether.

The 000 angle bonding is also based on the corresponding angle bending

in (CH3)20* By far the most uncertain frequency in the methyl ester.

 57
and the one having the greatest effect on the entropy, is the very

low frequency out-of-plane bending mode. This is essentially a

torsional motion of the skeleton of heavier atoms, namely,

% _ 0^

about the central bond. The reduced moment of inertia for this

motion should be of the order of 8 times the moment of inertia for

the torsion of the

H
0'

group in formic acid. As a rough approximation the force constants

ivill be assumed to be the same, and the frequency should then be

about 0.35 times the frequency of 232 cm“^ for formic acid (of above),

or about 80 cm“^.

The entropy contributions of the methyl ester vibrations on the

harmonic oscillator approximation are:

CH stretching (3) 0.00

CH bending (3) 0.05

GH3 rocking (2 ) 0.10

OC stretching 0.10

COC bending 0.97

Torsion 3.90

Total 5*12 cal/deg mole

To these vibrational contributions there must be added the

contribution of internal rotation of the methyl group. This may be

calculated from Table III of Pitzer and Qifinn^^^ if the reduced

 5B

moment of iiiertia 6f the rotating group and the barrier to internal

rotation are knowi. The moment of inertia for a methyl group is

—AO
about 5.4 X 10 e.g.s. units, leading to a calculated value of

3.77 for Pitzer and Gvdnn’s parameter Qf. Interpolation in their

table then jrields the follovdng values for the contribution of

internal rotation to the entropy, 3, at 300®K as a function of the

height of the potential barrier:

Potential Barrier Entropy

(cal/mole) (cal/deg mole)

0 3.64
360 3.60
600 3.53
900 3.40
1200 3.25
1500 3.08
1800 2.91
2100 2.74
2400 2.58
2700 2.43
3000 2.30
3600 2.07
4200 1.89
4800 1.74

Potential barriers for the rotation of methyl groups, as

determined from thermodynamic data for hydrocarbons, vary over the

range 0 (for dimethyl acetylene) to 4300 cal/mole in neopentane,

where there is apparently steric hindrance between the groups.

The case of a methyl ester is somewhat similar to propane, for which

the barrier is 3400 cal/mole. It would be preferable to use a value

derived from a compound in \diich the methyl group is bonded to an

oxygen atom, but the necessary data does not seem to be available.

It will be assumed that the barrier for a methyl ester lies in the
 59

range 2500 - 3500 cal/mole, corresponding to an entropy contribution

of 2.3 - 0.2 cal/deg mole.

Addition of the vibrational and internal rotational contributions

for the methyl ester now yields a total entropy contribution of 7*4

cal/deg mole at 300“K, Subtraction of the value 1.9 cal/deg mole

calculated above for the acid, yields 5.5 cal/deg mole as the entropy

increase in going from the acid to the ester at 300"K. This is to

be compared with the observed increase of 10.2 cal/deg mole at the same

temperature. The difference, 4.7 cal/deg mole, must be attributed either

to some additional increase for the ester, or to some factor such as

hydrogen bonding which decreases the entropy of the acid. The latter

possibility has been discussed above, and seems reasonable, although

it is not possible to estimate at all quantitatively the effect on

the entropy.

There is also a small entropy difference between palmitic acid

and sodium palmite. The probability of hydrogen bonding in the palmitic

acid crystal has been discussed above. Replacing the hydrogen with

sodium removes the hydrogen bond and substitutes an ionic bond. In

view of this change in the nature of the crystal it would be difficult

to estimate the magnitude of the entropy difference to be expected.

As seen from Table 13 the difference is not large,

(3) Suggestions for Future Work

It should be possible to compare the heat contents of delta

and omega sodium palmitate at room temperature. This might be done by

determining the heat of solution if a suitable solvent could be found.

 60
Another possibility would be to determine the heat effect involved in

heating each sample through the solid - subwaxy transition. One would

then kriow the A H for the hypothetical transformation of delta to

omega at room temperature. Ass’oming that the third law applies to the

two samples used in this research, the A S for the transformation

is given by these results. One could then determine A F by the

relationship

A F = AH - T A S,

Since the more stable phase must have the lower free energy, the sign

of this A F would indicate the relative stabilities of the two phases.

Extension of the heat capacity results to subwaxy temperatures would

enable one to determine A ^ 3-s a function of temperature. It would

then be possible to determine whether these modifications are mono­

tropic or enantiotropic, and, if the latter, to estimate the temperature

at which they would be in thermodynamic equilibrium.

A very interesting extension of this research would be the

determination of the heat capacity and heats of transition from room

temperature to 300°C. This should make it possible to describe the

changes in crystal structure occurring at each step in the melting

process. The usual method of determining heat capacity in this range,

by the use of an ice calorimeter, would not be satisfactory, as some

of the transitions are not easily reversible. An adiabatic method,

preferably with automatic temperature control, should be used. Ex­

tension of the measurements to the subwaxy range would also make

possible a third law check on the omega and delta samples.

 61

Free energies of formation of these compounds could now be

calculated if accurate heats of combustion were available. In order

to obtain free energies of formation with an error of one kilocalorie,

the heats of combustion would have to be determined with an error of

less than 0,05%»

 62

SUMMARY

1. A fractionating column for low pressure distillation has been

designed and built,

2. Palmitic acid has been purified by the fractional distillation

of methyl esters.

3. The heat capacities of palmitic acid and methyl palmitate have

been measured through the temperature range 15 to 300“K,

4. The heat capacities of the delta and omega phases of sodium

palmitate have been determined through the temperature range

60 to 300“K.

5. The thermodynamic function entropy, heat content, and free energy

function have been tabulated for temperatures up to 300°K,

6. The heat capacity of omega sodium palmitate is higher than that

of delta from 150 to 300"K. It seems likely that the delta phase

is more stable than the omega, but further data are required

before a definite conclusion can be drawn concerning the relative

stability of these phases,

7. The. heat of fusion of methyl palmitate and the heat capacity

of the liquid have been determined, but because of experimental

difficulties these data are not reliable.

 63
BIBLIOGRAPHY

1. Mays, G. W. - Ph.D. Dissertation, The Ohio State University (1953).

2. Wellman, W. W. - Ph.D. Dissertation, The Ohio State University (1950).

3. Buerger, M. J. - Proc. Natl. Aca. Sci., 28, 529 (1942).

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16, 175 (1948).

13. Wood, J. H, - Ph.D. Dissertation, The Ohio State University (1950).

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15.. Francis, F. and S. H. Piper - J. Am, Chem. Soc., 6l, 577 (1939).

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Jl, 1969 (1929).

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li, 1005 (1943).
 64
22. Weitkamp, A. W. and L. C. Brunstnm - Oil and Soap, IS, 47(1941).

23. Stedman, D, F. - Can. J. Res., 615. 383 (1937).

Weitkamp, A. ¥. and L. C. Brunstrun - U.S. Patent 2, 325,S19(1943).,

24. Althouse, P.M. and H. 0. Triebold - Ind. Eng. Chem., Anal. Ed,,
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Chem., 4 0 , 2379 (1948).

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Chemists Soc., 24, 257 (1947).

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2300 (1929),

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 65
AUTOBIOGRAPHY

I, John Walter Droege, was b o m in Seymour, Indiana, September

7, 1921. I received my secondary school education in the public

schools of that city. My undergraduate training was obtained at Indiana

University, from which I received the degree Bachelor of Arts in 1942.

After serving in the Army Air Forces for three years, I re-entered

Indiana University for one semester in 1946. That same year I entered

the graduate school of The Ohio State University. I have held a

research assistantship and teaching assistantships in physical chemistry

and quantitative analysis while completing the requirements for the

degree Doctor of Philosophy.