Michael J.
Joncich, The Thermodynamic Properties
Bruce H. Solko,
ond John E. Bower of Ammonium Carbamate
Northern Illinois University
DeKolb, Illinois 601 IS
An experiment in heterogeneous
equilibrium
T h e determination of changes of the
Gibbs free energy (AG), entropy ( A S ) , and enthalpy
( A H ) from measurements of the dissociation pressures of
pure solid compounds has been applied to oxides ( I ) ,
nitrides (t),carbonates ( S ) , and other compounds (4).
Experimentally, this involves simply the measurement
of the equilibrium pressure of the gas above the solid a t a
series of temperatures. For instructional purposes the
dissociation pressure as a function of temperature of
carbonates (5) and halides (6) has been used but these
experiments require high temperature furnaces, thermo-
couples, and potentiometers for temperature measure-
ment and reach equilibrium very slowly. An experi-
ment for determination of the properties of ammonium
Figure 1 . Dissociation presruro measurement apparatus. A, meter
stick; 8, 0-5O0C thermometer; C, " 0ring joint with clamp (not shown);
D, =ample container; E, stopcock.
598 / Journal of Chemical Education
carbamate utilizing- an inner isoteniscope has been de-
scribed (7).
We have recently introduced in the instructional
.
nhvsical
" chemistrv laboratow an ex~erimentof this ~ ~
type involving the decomposition of ammonium car-
bamate in which measurements are made in the range
30-5O0C with an ordinary 0-50C degree) ther-
mometer and utilizing an all glass apparatus. Very
reproducible results are easily obtaiued in one labora-
tory period.
With the apparatus shown in Figure 1, equilibrium is
reached in approximately 30 min.
Ammonium Carbamate Equilibrium
Measurements of the dissociation pressure of ammo-
nium carbamate which proceeds by the reaction:
NH4CO1NHds) * 2NHdg) + COdg)
have been carried out by a number of investigators (8-
I S ) . The most recent study of this compound by
Janjic (14) provided the incentive for including such an
experiment in our laboratory. We have experimented
with several different designs based on that of Janjic.
The one we have chosen is simple to construct, inexpen-
sive, easy to manipulate and is applicable to the study of
other equilibria of this type. Further, it has the advan-
tage that all of the solid and gas are a t thermal equilib-
rium with the constant temperature bath.
The dissociation of ammonium carbamate is treated
in detail in many elementary physical chemistry texts
( 1 5 ) . The equilibrium constant for the reaction is:
K, =~'~NH~PCOZ (1)
from which it follows that:
where P., is the total equilibrium pressure starting with
pure solid only.
The equilibrium may also be studied by admitting
definite known initial pressures of either NH3 or C 0 2 to
the evacuated vessel together with the solid. In such a
case, if x represents the initial pressure of NH3gas, it fol-
lows that
while if y represents an initial pressure of COz gas
Thermodynomic Considerations
The change in the standard Gihbs Free Energy AGOr
is then determined through the relationship
AG'T = -RT Ln K , (5)
where K , is the thermodynamic equilibrium constant.
The average enthalpy change is determined from the
relationship
I t follows that the average enthalpy change, a",
may be obtained by graphing in K , versus 1/T and de-
termining the slope, or from the equation
The entropy change may then he determined a t any
temperature in this range through the relationship
The Experiment
Ammonium carbamate was used as purchased with-
out further purification.'
The water jacket surrounding the sample container
consists of a glass bottle large enough to surround the
necessary equipment (Fig. 1) as well as the clamp re-
quired to compress the "0" ring joint (C in Figure 1).
The top of the bottle was fitted with a rubber stopper in
which three holes of the appropriate size were drilled.
The largest tubing is 20 mm in diameter; the reaction
vessel is 15 rnrn in diameter. To keep the rubber
stopper from springing out of place a clamp consisting of
two wooden collars (which could be bolted together)
may he necessary.
Prior to introduction of the sample the water jacket is
removed, the system is connected to a vacuum pump
through stopcock E, and the system is flamed gently
while being evacuated. The sample container is re-
moved, several grams of solid ammonium carbamate
added over a plug of glass wool, and the system is evacu-
ated for 10 min. The stopcock is closed and the solid
allowed to dissociate for 10 min. The system is evac-
uated again and the whole process repeated twice more.
Finally, while under evacuation the stopcock is closed,
the clamps and water jacket are put in place, and water
circulation from the constant temperature (*O.OlC)
bath is started. The bath is set for 30C initially.
Pressure readings may he taken at short intervals if it
is desired to study the rate of approach to equilibrium.
Otherwise only the final equilibrium pressure is re-
corded. Equilibrium is reached in approximately 30
min. Each equilibrium pressure is corrected for the
temperature effect on the Hg column height. The
exact temperature is read from the thermometer in
proximity to the sample. The bath temperature is then
raised by a small increment (3-5'C) and the series of
equilibrium pressures from 30 to 50C are obtained.
Since the apparatus from one period to another does
not actually require a new sample and re-evacuation, it
is a t equilibrium at room temperature when the student
We found that the ammonium carbamate obtained from
K & K Laboratories, Plainville, N. Y., provided the best results.
Samples from several other sources were tried.
Table 1. Equilibrium Pressures at Various Temperatures,
Log Equilibrium Constants, and AGTO
A .
--O D r
Temp. Pressure cal
(C") (Tom) Loe K. mole-'
begins. S x to eight additional points can thus be ob-
i
tained in one laboratory period. It is possible to em-
ploy the time between points to perform another experi-
ment simultaneously.
A simpler system which may be used as a semiperma-
nent setup was also devised. In this case the possi-
bility of leakage through the "0" ring joint or the stop-
cock was eliminated. This system was identical to the
other except that the "0" ring joint was not present and
the sample was contained in glass tube D before it was
sealed to the rest of the system. The purging cycle was
carried out as described previously and the tubing was
sealed off between D and E while under vacuum.
Results and Discussion
Table 1 and Figure 2 illustrate the experimental re-
sults of the average of five student experiments chosen
at random. A11 P., points from these experiments were
plotted versus T and the equilibrium pressures at 30,35,
40,45, and 50C were taken from the smooth curve con-
structed. For each value of log K , the value of AGO
was determined. A plot (Fig. 2) of log K , versus 1/T
was then constructed.
Figure 2. Log K, *enus 1/T X 10' for emmonium carbarnolo in the
ternperdure rongo of 25-50C. Data ore for Janjic l14), rquares;
Bennett, e l d.,(131, triangles; and student valuer, circle..
From the slope of the line in Figure 2, a0 is calcu-
lated to be 37.4 kcal mole-'.
Employing eqn. (8), AS"a t 25' is calculated to be
108.8 cal mole-' deg.-I.
In Table 2 values of AG0(25'C), AS,O and hRo are
compared with values calculated from the data of
Janjic (Ib), Bennett (I$), and with values calculated
from thermodynamic data tables (16). The agreement
is satisfactory. Our equilibrium pressures in many re-
peated trials were always larger than those of Janjic
Volume 44, Number 10, October 1967 / 599
Table 2. Comparison of Student and Literature Values of GREGORY, N. W., AND THACKREY, B. A,, J . Am. Chem. Soe.,
AGO, ASo, and AP(at 25'C) 72, 3176 (1950).
CAMPBELL, J. A,, J. CHEM.EDUC.,42, 489 (1965).
AGO @ AS" ROSE, J., "Advanced Physico-Chemical Experiments,"
John Wiley & Sons, Inc., New York, 1964, p. 304.
Student Values 4943 37.4 108.8 SAL~BERQ, H. W., MORROW,J. I., AND COHEN,S. R.,
Janjic (14) 5100 38.7 113 "Laboratory Course in Physical Chemistry," Academic
Bennett (IS) 4840 36.6 106.5
Thermo. Tables (161 4878 38.1 111.2 Press, Inc., New York, 1966, pp. 242-3.
BRINER,E., J . Chim. Phys., 4, 267 (1906).
MATIGNON, C., AND FREJACQUES, M., Bull. Sac. Chim.
(14). Our data agree rather well with the results of France, 31, 307 (1922).
Bennett (IS) except in the lower part of the temperature BRIGGS,T. R., AND MIGIDICHIAN, ~.V., J. Phvs. Chem.,. 28, ~

1121 (1924).
range where our results are slightly lower. TOKUOKA, M., J . Agr. Chem. Soc. Japan, 10, 1333 (1934).
The authors are grateful for the assistance of Mr. E. EGAN.E. P.. P o n s . J. E.. AND POTTS.G. D.. Ind. Eno.
J. Hyland in the development of the equipment and to , . . .
the Dean's Fund of Northern Illinois University. BENNETT.R. N.., RITCRIE.
~
P. -~
, -~ D.., Roannnnn. - .
~ n o & , J., T m s . Famday Soe., 49, 925 (1953).
D..
., A N D

Literature Cited JANJE,D., Helv. Chim. Acte, 47, 1879 (1964).

MARON, S. H., AND PRUTTON, C. F., "Principles of Physical
(1) OTTO,E. M., J. Electrochem. SOC.,112, 367 (1965). Chemistry," 4th Ed., The Macmillan Ca., New York,
(2) LORENZ, R., AND WOOLCOCK, J., Z. amrg. A11g. Chem., 176, 1965, pp. 246-7.
280 (1928). "Selected Values of Chemicd Thermodynemics Properties-
(3) LORENZ, 11.R.,AND JANZ, G. J., J . CHEM.EDUC.,40, 611 Part 1." Natl. Bureau Std. Tech. Note 27Ckl. Washins-
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