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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

T h e determination of changes of the carbamate utilizing- an inner isoteniscope has been de-
Gibbs free energy (AG), entropy ( A S ) , and enthalpy scribed (7).
( A H ) from measurements of the dissociation pressures of We have recently introduced in the instructional
pure solid compounds has been applied to oxides ( I ) , .
" chemistrv laboratow an ex~erimentof this ~ ~

nitrides (t),carbonates ( S ) , and other compounds (4). type involving the decomposition of ammonium car-
Experimentally, this involves simply the measurement bamate in which measurements are made in the range
of the equilibrium pressure of the gas above the solid a t a 30-5O0C with an ordinary 0-50°C degree) ther-
series of temperatures. For instructional purposes the mometer and utilizing an all glass apparatus. Very
dissociation pressure as a function of temperature of reproducible results are easily obtaiued in one labora-
carbonates (5) and halides (6) has been used but these tory period.
experiments require high temperature furnaces, thermo- With the apparatus shown in Figure 1, equilibrium is
couples, and potentiometers for temperature measure- reached in approximately 30 min.
ment and reach equilibrium very slowly. An experi-
ment for determination of the properties of ammonium 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
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

N. while under evacuation the stopcock is closed. points from these experiments were The top of the bottle was fitted with a rubber stopper in plotted versus T and the equilibrium pressures at 30. Equilibrium Pressures at Various Temperatures. tained in one laboratory period. or from the equation ploy the time between points to perform another experi- ment simultaneously. The system is evac- uated again and the whole process repeated twice more. Prior to introduction of the sample the water jacket is removed. versus 1/T stopper from springing out of place a clamp consisting of was then constructed.35. For each value of log K . two wooden collars (which could be bolted together) may he necessary. several grams of solid ammonium carbamate added over a plug of glass wool. *enus 1/T X 10' for emmonium carbarnolo in the ternperdure rongo of 25-50°C.-I. it compared with values calculated from the data of is a t equilibrium at room temperature when the student Janjic (Ib). The exact temperature is read from the thermometer in From the slope of the line in Figure 2. and AGTO The change in the standard Gihbs Free Energy AGOr is then determined through the relationship A . (5) (C") (Tom) Loe K. is satisfactory. Our equilibrium pressures in many re- Samples from several other sources were tried. Since the apparatus from one period to another does In Table 2 values of AG0(25'C).. The bath is set for 30°C initially. Each equilibrium pressure is corrected for the Bennett. Bennett (I$)..Thermodynomic Considerations Table 1. sults of the average of five student experiments chosen quired to compress the "0" ring joint (C in Figure 1). a". and the system is flamed gently while being evacuated. The agreement K & K Laboratories. In this case the possi- The entropy change may then he determined a t any bility of leakage through the "0" ring joint or the stop- temperature in this range through the relationship cock was eliminated.(131. Equilibrium is reached in approximately 30 Figure 2. The average enthalpy change is determined from the relationship I t follows that the average enthalpy change. provided the best results. The purging cycle was The Experiment carried out as described previously and the tubing was Ammonium carbamate was used as purchased with. Log K. is the thermodynamic equilibrium constant. a0 is calcu- proximity to the sample. Otherwise only the final equilibrium pressure is re- corded. the system is connected to a vacuum pump through stopcock E. triangles. Plainville. e l d. --O D r Temp. peated trials were always larger than those of Janjic Volume 44.Ol°C) bath is started. A11 P. AS. and 50°C were taken from the smooth curve con- The largest tubing is 20 mm in diameter. the clamps and water jacket are put in place. and with values calculated We found that the ammonium carbamate obtained from from thermodynamic data tables (16). A simpler system which may be used as a semiperma- nent setup was also devised. raised by a small increment (3-5'C) and the series of Employing eqn. S x to eight additional points can thus be ob- i may be obtained by graphing in K . The bath temperature is then lated to be 37.8 cal mole-' deg. A plot (Fig. rquares. To keep the rubber was determined. sealed off between D and E while under vacuum. Number 10. 1) as well as the clamp re.. which three holes of the appropriate size were drilled. AS"a t 25' is calculated to be equilibrium pressures from 30 to 50°C are obtained. and water circulation from the constant temperature (*O. and the system is evacu- ated for 10 min. min.O and hRo are not actually require a new sample and re-evacuation. 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. temperature effect on the Hg column height. the reaction structed. October 1967 / 599 .. 2) of log K . Finally. (8).4 kcal mole-'. It is possible to em- termining the slope. versus 1/T and de. begins. The stopcock is closed and the solid allowed to dissociate for 10 min. out further purification. 40. the value of AGO vessel is 15 rnrn in diameter.' The water jacket surrounding the sample container Results and Discussion consists of a glass bottle large enough to surround the Table 1 and Figure 2 illustrate the experimental re- necessary equipment (Fig. and student valuer.45. circle. Pressure cal AG'T = -RT Ln K . mole-' where K . Y. Data ore for Janjic l14). Log Equilibrium Constants. at random. 108. The sample container is re- moved. Pressure readings may he taken at short intervals if it is desired to study the rate of approach to equilibrium.

... Note 27Ckl. D. M. 28... AND THACKREY. N. Ind.. "Advanced Physico-Chemical Experiments. . Hyland in the development of the equipment and to . TOKUOKA. Inc.J.EDUC.. The authors are grateful for the assistance of Mr. J . Phvs. Japan. BENNETT. Chim. 1966.. A. Tables (161 4878 38. New York.. Soc. Famday Soe. Z. 1965... J. J.D. RITCRIE.6 106.S. ASo. Sac..1 111...R. J. D. H. C. New York. 49. M.. pp.. C. Washins- (1963). AND PRUTTON.T. 489 (1965). Chem. Bureau Std. BRINER. 925 (1953)... D: C. . E. Eno. R. Acte. 1961.. A11g.. J .. P o n s . "Selected Values of Chemicd Thermodynemics Properties- (3) LORENZ. ~ P. Comparison of Student and Literature Values of GREGORY. CHEM.. 600 / journal o f Chemical Educafian . S. Our data agree rather well with the results of France.Table 2. 1964. CHEM. J . (14). Agr. J.. Roannnnn.. 280 (1928). 4. Chemistry. range where our results are slightly lower." 4th Ed. I. 47. . Chem. Bull. MORROW. pp.8 SAL~BERQ. 176. Chem. W. E.V.E. AND FREJACQUES. A. .. The Macmillan Ca.. "Principles of Physical (1) OTTO. J.5 Thermo. EGAN.E... 246-7. 31. N. 11. M. Chim. J. 611 Part 1. CAMPBELL.4 108. ~ 1121 (1924). Electrochem. Chem. New York. T m s ... 304." John Wiley & Sons. G. . and AP(at 25'C) 72." Natl. Soe. Phys.. 307 (1922).R. ~ n o & . J. Bennett (IS) except in the lower part of the temperature BRIGGS. MATIGNON.." Academic Bennett (IS) 4840 36. Tech. -~ D..EDUC. Helv. A N D Literature Cited JANJE. Janjic (14) 5100 38.E.. p. R... J. AND MIGIDICHIAN. 1333 (1934).. amrg. Chim. F. H.2 Press. B.. 242-3. SOC. Inc.. 10. -~ . R.AND JANZ.. 3176 (1950). MARON..40. J. AND COHEN. J .. AGO...42. J. AND WOOLCOCK.7 113 "Laboratory Course in Physical Chemistry. 267 (1906). (2) LORENZ.. W. Student Values 4943 37.G. AND POTTS.. 367 (1965). ~. ton. the Dean's Fund of Northern Illinois University. Am. AGO @ AS" ROSE.112. P. 1879 (1964).