THE HEAT 0F ABSORPTION
0r
HYDRATED SILICA GEL
‘fEESIS FOR THE EEGBEE OF M. S.
M. M. Nasif
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THE HEAT 0? ABSORPTION
of
HYDRLEED SILICA GEL

L meeie
Submitted to the lunlty
of
MICHIGAN STATE COLLEGE

In Pertiel mnnment of the
Requiremente for the Degree
or

[enter of Science
Department of Chemistry

37 I
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IRE HEAT‘OP ABSORPTION OP HYDRAIED
SILICA GEL

HISTORICAL

A coneidereble enount of reeeerch hee been done
in recent yeere on the proPertiee of eiliee gel, eepeeielly
on ite property of edecrption. This property end releted
phenomene hee been investigeted extensively during recent
yeere in thie leboretory. in e continuation of thie work,
the heat of edeorpticn of hydreted eilice gel hee been
eerried out with the purpoee of determining the heat of
edeorption or the gel when it he: varying eeounte ct meter
on it. Alec the heat of edeorption of the gel wee
determined.in ecid end elkeline eolntione end detenlineticne
were made to determine if the gel edecrbed eny ecid or
eltely.

Petriek end Grin-I1 did eone work on the heet of
wetting of eiliee gel. They obteined veluee tor thie
property of the gel, ueing the following liquide: weter,
ethyl eleohol, eniline, benzene end cerbcn tetreehloride.
They did not eveouete their gel end they elec need gel
'hiob had been finely divided. Since the gel they need wee
not evecueted it would not be exPected thet their reenlte
were the nerd-nu. They conceived of eilioe gel ee to have
been e neee of eilice nuclei, eeoh nuclei being eurronnded

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with a thin film of water. Having such a conception of
silica gel they accounted for the heat of adsorption or
wetting on the basis of surface energy changes that took
place at the surface or each nuclei.

Inch research has been done on the heat of
adsorption of soils. Bouyouecs2 says that in the case
of soils the maximum is reached when the soil has been
heated to 107-c. for 24 hours. He also states that the
amount of water necessary to produce the heat is com»
putatively small. In an other article he says that the
temperature rise of water by sudden acmpressicn amounts
to 0.018'0. per lO atmospheres, and that the force of
compression rises to such large values as 156 atmospheres.

The heats of adsorption of some eleven organic
liquids on charcoal were determined by Lamb and Coolidgea.
They determined.the heats of adsorption by the expression
h -Ime; where h represents the heat of adsorption per
e.e. of vapor, x. the number of e.e. of vapor adsorbed,
and. m. and n characteristic constants of the vapor

adsorbed.

 

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APPIRATUS AND MATERIAL

Calorimeter:- A great deal of time was spent
in constructing a calorimeter that would be suitable for
this work. Several different types were tried but the
adiabatic type was the one finally used. The difference
in temperature of the outer and inner container was
never allowed to be greater than 0.06' and very often it
was less, and the time during which this difference
existed was very short. The time at which the two
containers are at maximum difference in temperature is
when the bulb containing the gel is broken and the
temperature of the liquid in the inner container goes
up suddenly. However, by means of a large resistance
used as a heating element, the temperature of the outside
vessel is brought up quickly so that there is no more
than c.05' difference between the two at any.time. All
parts inside of the calorimeter were made of glass with
the exception of the leads for the inside heating element.
These were made of copper of such size as to produce no
best when the current was flowing thru them. These leads
were also lacquered to prevent corrosion by the liquids.
The heating element in the inside vessel was a piece of
platinum about 5 cme. long soldered onto the copper
leads.

The outside of the calorimeter was an earthen-

 

were Jar about 16 inches tall and 10 inches in diameter.
Inside of this Jar was an inverted bell-Jar. The space
between these two vessels was filled with saw-dust and
the tsp of the saw-dust filling was covered with a
coating of paraffin to prevent an air current. This
vessel was covered with a round piece of one inch board
which fitted over the top very tightly. Thru this cover
was a two inch hole in the center to allow the stirrer
and the thermometer of the inside container to project
out of it. There was also a hole for the stirrer
thermometer, and leads for the heating element. Inside
of this container was an evacuated Dewar flask about

12 inches tall and 1 6/8 inches inside diameter. This
was supported in the center of the inverted bell-Jar and
weighed down by means of a heavy lead weight. The space
between the Dewar flask and the bell-Jar is filled with
distilled water.

Preparation of Gel:- The gel used was a product
of The Silica Gel Corporation and was of good quality.
All samples of gel were first freed of any particles that
were brown or discolored in any way and also particles
that were of a white color. Only the clear transparent
particles being used.

Approximately 8.6 g. samples of the gel were

used in all cases. The gel was treated under different

 

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conditions with different experiments, the results being
that the different samples under different conditions of
treatment giving different values for the heat of adsorption.
The samples of gel were placed in glass bulbs which were
blown so that the wells became very thin, yet were strong
enough to withstand being evacuated. These bulbs were

then sealed off fram the air with the gel in them.

One experiment was performed with several samples
of gel Just as the gel was received, that is, without
being treated in any way, using water.

Other experiments were done using several
samples of gel that had been (1) heated for 84 hours at
120cc., (2) for 4 hours at 250' and evacuated at the same
time, and {5), evacuated for 1 hour without heating
and combinations of heat and vacuum, the purpose being to
get samples of gel with varying water content.

The above experiments were repeated using
0.2 N Hz 804 solutions in place of water.

The water used was distilled laboratory water
which had been redistilled, and the sulfuric acid solution
was made of this water and C.P. Hg 80‘.

The thermometers used were Bureau of Standards
thermometers. The one in the outside vessel being
graduated to 0.1., and the one used on the inside of the
Dewar flask being graduated to 0.01'.

Method of Prodedure:- The liquid whose heat
of adsorption was to be determined was put into the
Dewar flask. Then the bulb containing the gel was put
into the flask and the glass rod with a loop on the end
of it was placed over the bulb to hold it down and keep
it from getting in the way of the stirrer. Then the
stepper with the thermometer, stirrer and thermo-element
sealed in it was put into the flask. The flask was then
put into the outside bath. The temperature was brought
to the temperature of the liquid in the flask either by
cooling or heating, as the case may be, during which
operation the stirrers in both vessels being in motion.
The temperature of the liquid in the flask was then noted
and recorded. Then the bulb was broken and the temperature
was noted every five seconds by means of a step-watch
until a constant temperature was attained. The thme required
for this rise in temperature was noted. Then enough heat
was introduced into the system to produce the same rise
in temperature in the same length of time. This was
accomplished.by allowing a current from a 4 volt lead
storage cell to pass thru a rheostat, a standard
resistance and the thermo-element. The current was so
adjusted that it would produce the same rise in temperature
in the same length of time that the gel did. In this way

all losses were corrected. The current was measured

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by noting the potential drop across the standard
resistance of 0.1 ohm by means of a type K polentiometer.
Then the potential dr0p across the thermo-element was
measured in the same way by throwing the switch in the
other direction. Knowing the current and the potential

drOp, the resistance can be calculated.

Method of Calculating the heat of adsorption:-
Joule's law states that

 

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Knowing the current, potential drOp and the
thme, the amount of heat introduced into the system can be
calculated. How this gives the number of calories pro-
duced by the current and which caused the liquid in the
calorimeter to rise the same number of degrees in the same
length of time as the gel did. It is necessary to use a
current of such value that it will produce the same rise
in temperature in the same length of time as the gel, so
that losses due to conduction and radiation will be
accounted for.

This heat is due to all the gel added. How
to obtain the heat due to one gram of gel or the heat of
adsorption of the gel, it will be necessary to divide the

total amount of heat by the number of grams of gel used.

E I t
4.183

 

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where g is the number of grams of gel added.
The results obtained are tabulated as

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19
DISCUSSION

It is a well sstablished fact that water adsorbed
on the surface of a solid, such as silica gel, has
undergone a thermodynamic change in state and is held
on the surface by an enormous force. SOme of the early
investigators to advance this theory are Jungh4,

.Rose5, and Parksa. This has been more recently continued
by latrick and Grimm1 and Lamb and Coolidge3 by their
data on the heat of adsorption of water.

It is quite apparent that the heat of adsorption
is due to a change of concentration of the molecules of
the liquid at the surface or in the pores of the gel.

This has been recently continued by Ewing and Spursay7

in their determination of the density of water adsorbed
on silica gel. They found that the density of water
increased when adsorbed on silica gel up to the value
1.6869 g. of water. They noticed that heat was

liberated when the gel was allowed to absorb water, but
they did not make any measurements on it. They found a
close correlation between the density values for 1.6867 g.
and 0.6367 g. of adsorbed water which, they said, _
indicated one phase of water on the gel. The mean density
values for the two larger quantities of adsorbed water

are less than the density of liquid water at the operating

20

temperature, indicating the presence of three phases

of water: compressed water, liquid water, and water
vapor. This water vapor, they said, exerts only a low
vapor pressure; hence, all three forms of water are held
on the gel under pressure.

Then by calculations based upon the volume of
the adsorbed water in the runs where the silica gel
contained 1.6867 g. or 0.6357 g. of water, and a
correlation of Bridgeman's compressibility data, it was
shown that in these cases the pressure on the adsorbed
water was of the magnitude of 750 atmospheres.

Thus, when the molecules of water are compressed
at the surface or in the pores of the gel, there is a
decrease in the kinetic energy of the molecules. In
order to have a decrease.in the kinetic energy,heat is
liberated which is an increase in the potential energy
of the molecules. This is the Opposite of such phenmmena
as latent heat of vaporisation, in which case the molecules
are driven farther apart due to the addition of heat to
the system and the heat being transfonmed into kinetic
energy of the molecules. The forces acting in this
phenomena are the stray fields around the molecules of the
wetting substance and the molecules of the substance
being wetted. The greater these stray fields, the less
the tendency to exhibit this phenamena.

21

The results given in Tables I to IV inclusive,
were obtained.with a gel that had a maximum water content
of 6.2%. The results indicate that there is a general
lincrease in the heat of adsorption as the water content
of the gel is decreased. The results given in Tables
7 to II inclusive, show somewhat the same thing. There
is a decided increase in the heat of wetting between
the gel containing 16.6% water and the gel containing
8.6%Iwater. But there is a large difference in the heat
of wetting of the gel with 8.5% and that with 3%. u
the water content decreases below 3%, the heat of wetting
again increases rapidly until the maximum ralue is
reached. It is interesting to note that the largest
rise in temperature took place very shortly after the gel
was exposed to the liquid and that this initial rise in
temperature was larger and took place acre quickly with
the gel that had the smaller'asounts of water on it. we
obtained.acre nearly a wetting of the gel by the liquid,
as indicated by the results given in.Tebles IV and IX,
because when the gel is heated and evacuated, the water is in
the gaseous state, and a smaller quantity can be held,and
is probably held, on the surface of the gel. new, when
the gel is again cooled, the water becomes liquid and
occupies a.much smaller volume than when in the gaseous

state. This condensation of the gaseous water leaves a

88

large portion of the surface of the gel with nothing
adsorbed on it. This free surface then absorbs the
liquid with great rapidity and liberates a large amount
of energy. The larger this free surface the greater the
amount of energy liberated.

According to Patrick and Grimml, in order to
get a heat of wetting of 19.22 Cal. per gram of gel
it is necessary that the gel exhibit a surface of 6.9 x
107 cm.3. which is an enormously large surface. It is
evident that the surface energy is therefore sufficient
to explain the observed heet effects.

Lamb and Coolidge3 in their determinations on
the heat of adsorption of vapors on charcoal have
calculated that the amount of carbos disulfide adsorbed
on a gram of charcoal is 0.4 cc at atmospheric pressure
and about 0.26 so under a pressure of 37,000 atmospheres.
The carbon disulfide was sufficient to fill all the
capillaries which had a volume of o.cs cc. Assuming the
capillary area to be 100 square meters and that the
thickness of a molecular layer is l x 10"8 cm., then the
above amount of carbon disulfide if spread over the whole
surface would have given a layer ‘0 molecules deep.

Lamb and Coolidgea regard the heat effect as
due to two factors, the heat of liquefication of the gas

and the heat effect due to further compression of the

liquid.by the adhesive forces of the adsorbent. The
latter or not heat of adsorption, is equal to the heat
of wetting at the saturation pressure of the liquid.
Barkins and Ewihge have obtained direct
experimental evidence of the compression of a layer of
liquid adsorbed on a solid in the case of activated
charcoal and organic liquids. The attractive forces
between the charcoal and the various liquids are shown
to be constant and of the order of 30 to 40 thousand a
atmospheres, in agreement with the findings of Lamb and
Coolidge3. It is pointed out that experiments on the
internal pressure of the liquids have not succeeded in
demonstrating pressures higher than 78 atmospheres.
Harkina and.Ewing derive the heat of ‘
adsorption of a liquid.by a solid from surface energy
considerations as follows: If we consider that the
solid is immersed in the liquid against air, the net
result is that the surface of the solid is replaced by a
solid - liquid interface. The heat of adsorption,
«as, is then equal to the total -ount of energy given
off in the process when carried out isothermally,
ls, or

-Qa - Is - Es - Ed

Where Is and Bi are respectively the total

energies of the solid surface and of the interface.
The heat of adsorption of a liquid on a solid has
always been found to be positive, indicating that the
total surface of the solid is greater than that of the
interface.

Table III is a emery of the results given
in Tables V to 11 inclusive.

In Tables 1111, XIV, and IV are given the
results obtained by wetting the gel having the indicated
water contents with approximately 0.8] sulfuric acid.
These results agree very well with those obtained for
water and gel having on it the same amount of water.
This indicates that the presence of sulfuric acid
does not effect the heat of wetting of the gel. The
acid was analysed before and after it was exposed te the
gel, and it was found that the concentration increased
from 0.19330 before exposure to 0.1986 after exposure.
This indicates that water and not sulfuric acid was ad-
sorbed by the gel.

Bartell andiliiller9 in their work on the
adsorption by sugar charcoal of acid and basic dyes
say that inorganic acids are but comparatively slightly
adsorbed by charcoal because the inorganic onion
replaces more feebly the on; ion. Inorganic bases
are adsorbed scarcely at all, owing to the fact that

metals less noble than H do not replace 3’ frmm Carbon.

25

Silica gel does not seem to have an affinity
for acid radicals much the same as carboh.

in attempt was made to obtain the heat of
wetting of silica gel with sodium hydroxide solution
but no constant temperature could be obtained which

indicated that the alkaly reacted with the gel.

26

SUMMARY

1. Some heats of wetting of silica gel with
water were obtained with the gel containing varying
amounts of water on it.

2. The heat of wetting increased more rapidly
as the amount of water on the gel became smaller, that
is, there was a very large increase in the heat of
wetting between the gel that had 1% water on it and the
gel that had very little or no water on it.

3. The heat of wetting of a 0.2N solution
of sulfuric acid was obtained and found to be the
same as for water along.

4. No value for the heat of wetting of
sodium hydroxide was obtained because it was thought
that the alkaly reacted with the gel.

1.

2.

3.

4.

5.

6.

8.

27

REFERENCES

ratriok and Grimm
3001‘. me Cheme SOC. 45,3144 (1921)

Bouyoucos
Technical Bulletin No. 42,
Soil Science, Vol. 17, No. 2, tab. 1924,
Soil Science, Vol. 19, No. 2, 1926,

Lamb and Coolidge
Jour. Am. Chem. soc. 42, 1146 (1920)

Jungh,
Ann. Phys. Chem. 126, 292 (1865)

Rose,
Ann. Phys. 73, l (1849)

Plrkl.
Phil. Mat. 4, 820 (1902); 5, 617 (1905)

Harbins and Ewing
JOlir. we Chemo SOOe 43, 1795 {1921)

Bartell and M1110!
Jour. Phys. Chem. 28, 992 ~ 1000 (1924)

 

   
 
    
 
  
   

   
    
 
  

     

   

  
  

    
   
 
  

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