J. Chern. Tech. Biotechnol.

1980,30, 85-101

Phase Equilibria in Ammonia-Carbon Dioxide

Systems at and above Urea Synthesis Conditions
Saul M. Lemkowitz, Jan C. van Erp,a Domien M. Rekers
and Pieter J. van den Berg
Luboratory of Chemical Technology, Devr University of Technology, Delft, The Netherlands
(Paper received 29 ApriI 1979 and accepted 15 October 1979)

A comprehensive temperature-pressure-composition phase model is presented

which combines all known phase equilibria relating to the binary ammoniaxarbon
dioxide system (no urea present) at urea synthesis conditions. The bubble-points and
critical-points of the ammonia-carbon dioxide section of the ternary ammonia-water-
carbon dioxide system at chemical equilibrium (urea present) have been measured up
to the values of NH3/COz=2, T=280"C, and p=2OOO atm. The critical tempera-
ture and pressure values of a NHa/COz=2 mixture, of importance t o the theory
describing the maximum conversion to urea, have been found to be 276°C and
1250 atm, respectively.

1. General introduction
Knowledge of the phase equilibria of the ammonia-carbon dioxide system is of great importance
to the urea industry and of interest to the field of heterogeneous equilibria involving chemical
reactions. In studying the phase equilibria of ammonia, carbon dioxide and their reaction products
we begin with the phase rule
F=C+2-P (1)
where F is the number of intensive thermodynamic properties necessary and sufficient to define
the state of the system (degrees of freedom), C is the number of components necessary and sufficient
to describe the system and P is the number of phases present. In applying the phase rule, the chief
problem is that of determining the number of components. For a system involving a chemical
reaction, it may be shown that'
C = C'- R - Q (2)
where C' is the number of chemical substances (constituents) present in the system, R is the number
of independent, reversible chemical reactions occurring between C', and Q is the number of restric-
tive equations.
Ammonia and carbon dioxide react spontaneously and reversibly to form ammonium carbamate
2(NH3)g + (COZ)~S(NHZCOONH~)I
AH= - 100.4 kJ mol-1 (T= 167°C. p = 140 atm)

in which 1 and g refer to the liquid and gas phase, respectively, A H to the reaction enthalpy, K to
the reaction equilibrium constant, and the formulae between parentheses to the activities of the
11 Present address: Imperial Chemical Industries, Rozenburg, The Netherlands.
0142-0356/80/0300-0085 302.00 01980 Society of Chemical Industry
85
5
86 S. M. Lemkowltz et al.

constituents. At temperatures below about 130°C ammonium carbamate is the only reaction pro-
duct formed. Then C'= 3, R = 1 and C = 2: the system is a two component one. The phase behaviour
of this binary system can be presented using the ammonia-carbon dioxide composition plane to
express component (but not constituent) concentration.
However, at high temperatures, especially above about 140-1 50"C, ammonium carbamate
reacts spontaneously and reversibly to form urea and water
+( H z o ) ~
(NH~COONH~)I*(NH~CONH~)I
AH-27.6 kJ mol-1 (T= 180°C)

Ks= (NHaCONHz)i(H20)
~- _.
1

(NHzCOONH4)i
Then C'=5 (NH3, CO2, H20, NHzCOONH4, NHzCONHZ),R = 2 [equations (3) and (6)] and
therefore C= 3 : the system is a three component one i.e. ternary. If we choose as the three com-
ponents NH3, COa and H20, then theconstituents urea and ammonium carbamate can be represented
(in terms of the components) by means of the equations
NHzCOONH4= 2 NH3 COs + (9)
NHzCONHz=2 NH3+COz-H20 (10)
If the system is initially composed of only carbon dioxide and ammonia and the conditions of the
system are such that only one phase is present, e.g. the liquid phase, then the water concentration,
in terms of water as a component, is zero. This statement is true because each mol of water originat-
ing from the eventual formation of urea [equation (6)] is cancelled by the negative mol of water
necessary to express urea concentration [equation (lo)] in terms of its component composition.
Under these special conditions (an initial composition of only ammonia and carbon dioxide and
only one phase present) we can represent the component concentration of the ternary system making
use of the binary ammonia-carbon dioxide plane.
It is essential to distinguish between the two systems under discussion, one without urea (a binary
system), the other with equilibrium concentrations of urea (a ternary system), because they exhibit
a very different physical and chemical behaviour. In section 2 of this paper the former case will be
discussed and in section 3 the latter case. Strictly speaking, in section 2 we are discussing the com-
plete binary N H 4 0 2 system; in section 3 we are discussing that part of the ternary NHs-H20-C02
system in which the component composition can be represented using the NHrCOa composition
plane.

2. A temperature-pressuremposition phase model for the NHFCOZ system

A knowledge of the phase equilibria of the binary NHJ-COZsystem is essential for achieving the
optimal conditions for the recirculation section of urea synthesis plants. Because of its technical
and scientific importance many researchers have investigated the behaviour of this system. However
as yet no systematic study of the N H d O z system as an entity has yet been published. We now
examine data in the literature in the light of the theory of phase equilibrium diagrams314 and
attempt to organise this information into a temperature-pressur-omposition phase model in
which all known phase data can be incorporated in a comprehensive and logical manner. This
discussion is based in part on unpublished studies.5
Because of the significant chemical differences of the two components, NH3 being a highly polar
substance of basic character and CO2 being non-polar and slightly acidic in character, and because
of the large difference in volatility, the system N H d 2 0 2 exhibits complex phase behaviour, such as
(i) NH3 and COZreact to form a dissociating compound, ammonium carbamate [equation (3)];
(ii) the formation of the relatively involatile ammonium carbamate leads to the occurrence of a
maximum temperature (minimum pressure) azeotrope in the liquid-gas planes; (iii) in the
NHs-rich area (relative to ammonium carbamate) liquid immiscibility occurs; (iv) in the COz-rich
Phase equilibria in ammonia-carbon dloxide systems 87

area a lower critical end-point is found i.e. above this temperature solid ammonium carbamate
coexists with super-critical COz. In the following sections these phenomena will be examined in
some detail.
The dissociation pressure of ammonium carbamate has been studied by a large number of
researchers. Gmelina presents an exhaustive summary of the published results up to about 1936
and in 1967 Chao7 presented a detailed review of the more recent literature. The most important
studies of this compound have been made by Briggs,8g Egan,lo Bennettll and Joncich.lZ Eganlo
has shown that up to about 100°C the literature discussing the vapour pressure is in good mutual
agreement and can be described by the relationship
lOgp= -2742/T+11.1448 (1 1)
(p in mmHg, T in K). Briggse and Swets13 derived a formula for the pressure-temperature-
composition relation of the condensation pressure (to solid ammonium carbamate) of NHwCOZ
gas mixtures, based on the assumption of ideal gas behaviour and the absence of association of
NH3 and COz in the gas phase (this last fact being substantiated by studies reported by Gmelins
and, more recently for much higher pressures, by Effremova and Leontieval4). This formula is
lOgp= -2741.9/T+7.9876- 1/3 log [ YNHS2 (1 - YNHj)] (12)
in which p is the condensation pressure in atm, T is the temperature in K and Y N H ~is the gas
phase mol-fraction of NH3.

Table 1. Maximum sublimation point of ammonium

carbamate

Temperature Pressure
Researcher ("C) (am)

BrinerI3 152 83.4

Frejaquesl6 155 -
JaneckeI7 153 88
Terresl8 147-150 -
Kaasenbrood 153 81
ScheffersE 152 84

It should be noted that at higher temperatures

(7-5130°C) the study of ammonium carbamate is
complicated by the occurrence of the urea reaction. The
values of T = 153°C and p = 8 7 atm are chosen as the
values of the maximum sublimation point.

Ammonium carbamate is a dissociating binary compound3a. 48 and as such its behaviour must
be seen as a part of the NH3-CO2 system. In general a dissociating compound does not, like a
normal pure substance, exhibit a triple-point (at a certain T and p) but rather a temperature-
pressure interval in which solid, liquid and gas phases can exist simultaneously in mutual
equilibrium. The starting-point of this interval is called the maximum sublimation point (MSP)3bs 4b
and is the maximum temperature and pressure at which gas and solid can coexist in the absence of
liquid. The end-point of this interval is called the minimum melting point (MMP)3b, 4b and is the
lowest temperature and pressure at which liquid and solid can coexist in the absence of gas. The
MSP, often incorrectly referred to in the literature as the 'melting point', has been measured by a
number of researchers, whose results appear in Table 1.
The MMP is unknown and is impossible t o measure due to the rapidity of the urea reaction at
temperatures above the MSP. For simplicity the MMP has been arbitrarily chosen as occurring
at 156°C and 110 atm.
88 S. M. Lemkowitz et a/.

The NH3-side (relative to ammonium carbamate) of the NHs-COz system is fairly well known.
Solid ammonium carbamate dissolves poorly in liquid NH3; therefore the three phase line SAC-
12-g is only slightly lower in pressure in the p-T projection than the vapour-liquid line of pure
NH3. The composition of 12 has been estimated to be 98 mol-% at 116"C5~17 and the solubility of
ammonium carbamate is probably even less at lower temperatures; the composition of the gas
phase is practically pure NH3. The quadruple-point SAC-11-12-g of the system has been estimated
to occur at l16-120°C5v 171 2 0 and 83 atm, which is just slightly less than that of saturated NHs
at this temperature. At these conditions a second liquid phase, 11, is formed whose composition
has been estimated to be about 78 mol- % NH3.l' As has already been mentioned, 12 is nearly pure
NH3, and the three phase line 11-12-g therefore lies only slightly below the 1-g line of pure NH3.
The NHs-COz system thus exhibits an area of liquid immiscibility (h+h). At a given temperature
the area of immiscibility in the pressurecomposition plane decreases with increasing pressure (as
has been found at our laboratory) and ends at a critical point, 11= 12. The pressure, temperature and
composition values of this critical line are unknown and have been drawn arbitrarily in Figures
1 and 2. In the projection the quadruple point SAC-11-12-g is formed by the intersection of the four
three-phase lines SAC-11-12, SAC-ll-g, SAC-12-g and 11-12-g. Since 12 is almost identical to pure

TemDeroture -

S ~ ~ ,

Figure 1. Schematic pressure-temperature-composition projection of the binary ammonia-carbon dioxide

system (no urea present). AZ refers to the azeotropic composition and AC to the composition of ammonium
carbamate. The solid squares, triangles and circles refer to quadruple points, triple points and points, respectively,
formed by the tangency of a two-phase line with a three-phase line.
Phase equilibria in ammonia-carbon dioxide systems 89

240

200

160
-E
-c
0

I20

a0

40

d
n
" an 200

I I I 1 I I I I I

I" 40
2o t
Z
$
5 60
z
80

I00

Figure 2. Semi-quantitative pressure-temperature-composition projection of the binary ammonia-arbon

dioxide system (no urea present). - , Measured; - --- and ---*-, estimated.

ammonia, it is reasonable to assume that the three phase. line 11-la-g ends a t the critical line 12= g,
which begins at the critical point of pure ammonia. The temperature and pressure values of the
end-point will be only slightly higher than the values of the critical point of pure ammonia, and the
composition at intersection will be very near the ammonia composition axis. With the assumption
of the critical end-point Icg near the ammonia axis and the existence of the quadruple-point it
is further assumed, making use of the principles of phase diagram theory,g~4 that the three phase
line SAC-11-18 intersects the critical line 11= 12.
90 S. M. Lemkowitz cr at.

For urea technology the most important line in the NHs-COz system is the azeo-
tropic line.2*2 1 v z2 Operation of the high pressure condenser section at azeotropic conditions
results in condensation at the highest possible temperature (at a given pressure) leading to the
production of the highest quality process steam. Since azeotropic condensation occurs without
the occurrence of diffusion limitation through a non-condensing gas, the condenser operating at
azeotropic conditions is also of minimum size. In practice water is always present together with the
ammonia and carbon dioxide entering the condenser. Quantitative studies of the effect of water on
the condensation have been performed.23
The T-p-X values of the azeotropic line have been reported by VerstegenZ4and are incorporated
into Figures 2 and 3 presented here. The azeotropic line begins at 147°C and 70 atm at the three
phase line SAC-Il-g, which itself begins at the quadruplepoint. The azeotropic composition becomes
increasingly NHa-rich with increasing temperature. Because the azeotropic line is originally tangent
to the three phase line SAC-h-g, and because the pressure value at this point of tangency is lower
than that of the quadruple-point and the MSP, the SAC-11-g line will probably exhibit a pressure
minimum, as is shown in Figure 1.
The COz-side of the system (relative to AC) is almost completely unknown. Because of the large
temperature difference in the m.p. of CO2 and the MSP of AC, and because of the almost com-
plete insolubility of AC in liquid C02 a first critical end-point (P) is found almost at the critical
point of COz itself (Tc=31.O0C.pc=72.9 atm); at this point solid AC is in equilibrium with a
critical gas-liquid mixture. The SAC-1-g line practically coincides with the vapour line of COZ and
the gas and liquid phases consist of practically pure C02. At temperatures above P, solid AC is in
equilibrium with a fluid phase consisting largely of C02. The p-T-X values of the second critical
end-point (Q)have been arbitrarily chosen. Because of the very large differences in the tem-
peratures of the triple point of C02 (-56°C) and the MSP of ammonium carbamate, it is
not improbable that the COz-AC area of the NHFCOZ system exhibits behaviour of the type
CO~-diphenylamine,~d, 4c rather than of the type ether-anthraquinone (both these types of be-
haviour describe systems in which a solid coexists with a fluid phase).4d Behaviour of the former
type implies that the second critical end-point ( Q ) is likely to occur at very high pressures. The
path of the critical line also implies metastable liquid immiscibility in this COz-rich area. Because
of the impossibility of measuring such behaviour (due to the occurrence of the urea reaction and
subsequent further decomposition reactions) and its lack of practical importance, no further dis-
cussion of this area will be attempted and ether-anthraquinone behaviour will be assumed for
simplicity.
Such behaviour is qualitatively presented in a temperature-pressurecomposition projection in
Figure I, in which for clarity, the p-T-X differences of the three phase lines are exaggerated relative
to the phase lines of the pure components. In Figure 2 a quantitative projection is attempted. In
this projection many of the three phase lines simply coincide with the phase lines of COz and NH3.
A beautiful and clarifying three dimensional phase model of this complex system has been prepared
at the Laboratory of General and Inorganic Chemistry of the University of Delft by Professor
G. A. M. Diepen, J. N. Broers and J. Ruis.
The practical use of such phase diagrams is illustrated in Figure 3 in which a quantitative tempera-
ture-composition diagram ( p = 140 atm) is presented; ideal condenser conditions occur at AZ, the
azeotropic point. As already stated, the binary N H 4 0 2 system illustrates extremely complicated
phase behaviour. A qualitative pressure-composition diagram ( T = TI in Figure 1) illustrating such
behaviour is presented in Figure 4.

3. The phase behaviour of ammonia-carbon dioxide mixtures at chemical equilibrium (urea present)
located on the amrnonia-carbon dioxide composition plane
3.1. Introduction
From both the technological and scientific viewpoints the high temperature ( T > 130°C) phase
equilibria of mixtures located on the NH3-CO2 plane are important. Values of the bubblepoint
Phase equilibria in ammonia%arbon dioxide systems 91

I70

A2

165

I60

- 155
I

0
0

-L
E
?
:

-12

I I
I I
I
AC
I I I t I
20 40 60 80 I I
Mol Oh NH,
Figure 3. The binary ammonia-carbon dioxide system (no urea presnt) at 140 atm. The top half of the figure is
quantitative; the bottom half is schematic. In the top half the bold line is the dew-point line, the fine line the bubble-
point line.

pressures, essential for the design of the urea synthesis reactor, have been measured in the pressure,
temperature and composition range of 20 < p < loo0 atm, 130 4 T <240°C and NH3/COz = 2.5
to 100% NH3, respectively.25. 26 In this same area liquid densitiesz7 and the critical line have also
been nieasured.25~z6 Data concerning the effect of addition of waterz5*28 (molar HzO/COz >O)
and ureazb, 28-90 (molar HzO/C02 < 0) on the phase behaviour of such mixtures are also available.
A comprehensive ternary phase model25. z8. 31 and thermodynamic analysesz5. 3z-34 of these
mixtures within the ranges mentioned are in the literature.
For the urea industry, it is obvious that it is also necessary to know the equilibrium urea con-
centration i.e. the equilibrium conversion t o urea as a function of initial composition, temperature
and pressure. These equilibrium conversions have been most recently investigated by M a v r o v i ~ , ~ ~
Inoue ef al.,36and Kucheryavyi ef al.S70 38 These researchers are in reasonable agreement up to
about 190-20O0C, but thereafter disagreement is pronounced. Mavrovic35 predicts continuously
increasing conversion with temperature while Inoue et al.36 and Kucheryavyi et al.37.38 find
conversion maximum with respect to temperature (the absolute agreement between these last two
92 S . M. Lemkowitz ct a/.

DY
1,=1*
12 + 9

Figure 4. Schematic pressure-composition figure at

AC constant temperature ( T = T l in Figure 1) for the

Mol NH, - binary ammonia-carbon dioxide system.

research groups is, however, not good in the high temperature range). It is now generally accepted
that a conversion maximum with respect to temperature definitely exists in the liquid
What causes this conversion maximum, and is this maximum related to the phase equilibria of
the system? Inoue et U I .ascribe
~ ~ the conversion maximum to the opposing effects of temperature
on equations (3) and (6), the two independent but coupled reactions which determine the equilib-
rium concentration of the constituents. The law of Van’t Hoff predicts that the equilibrium constant
of equation (6), Ka, increases slightly with increasing temperature. The equilibrium constant for
the formation of ammonium carbamate under high pressure conditions, Ks,falls sharply wth
increasing temperature. At low temperatures KS is large (% 1) so that the weakly positive dKa/dT
term is controlling for the urea conversion. At high temperatures (above about 2OO0C), however,
the fall in the value of KSbecomes so large that the strongly negative dK3/dT term becomes control-
ling. The authors agree with this explanation but also believe that the approach to critical conditions
plays a secondary but simultaneous role; as critical conditions are approached, all of the mixture’s
properties, including the urea conversion, become pressure functions. Evidence for this hypothesis
has been presented previously.27
In a fairly recent articles9 another explanation has been proposed. In a largely theoretical study
based, in part, on critical measurements performed by the present authors,26 it is concluded that the
conversion-temperature maximum is indeed caused by the approach to critical conditions. Mainly
on the basis of theoretical considerations it is argued that an equilibrium NH&Oz= 2HzO/COz
= 0 mixture at critical conditions has the same critical properties as pure undissociated ammo-
nium carbamate (supposedly stable at critical conditions). More generally, as an NH3-4202 mixture
(NHs/COz > 2) at equilibrium approaches critical conditions equation (6) proceeds rapidly and com-
pletely to the left leading to a zero urea conversion at critical conditions. Thus at critical conditions
the reaction mixture consists exclusively of undissociated ammonium carbamate and excess (free)
ammonia. It is this effect which causes the conversion-temperature maximum. Interestingly enough
in a more recent article40 the conversion-temperature maximum is ascribed to the sharply increased
activity of water at high temperatures, which lowers the urea concentration [reaction (6)].
Phase equilibria in ammonia-carbon dioxide systems 93

Careful analysis41-42 of reference 39 shows it to consist of a combination of a number of classical

methods. These are the empirical law of Cailletet and M a t h i a ~(to~ estimate
~~ the critical density
from density measurements near the critical point), the method of J0ffe43 (to estimate the critical
conditions of a binary mixture from the critical values of the components), the simplified integrated
form of the Clausius-Clapeyron equation"8 (as is often used to calculate heat of vaporisation from
vapour pressure data, assuming ideal gas behaviour) and correlations of the Cox-Othmer type47b
modified by the law of corresponding states for use at near critical conditions (to correlate vapour
pressure data up to the critical point). A weak link in these methods is the use of the vapour pressure
of ammonium carbamate to calculate its heat of vaporisation. Firstly, the gas phase is so non-
ideal at the high pressures involved ( p > 800 atm) that the use of the simplified Clausius-Clapeyron
equation to calculate heats of vaporisation leads to very large errors. Secondly, values for the
vapour pressure of ammonium carbamate are cited for temperatures of up to 283"C, while accurate
vapour pressures for this substance are known only along its sublimation line, i.e. to about 155"C.7
At about 155°C ammonium carbamate reacts very rapidly to urea and water so that vapour pressure
measurements become impossible.
In their theory to explain the conversion-temperature maximum, Kucheryavyi et al. predicted
the critical conditions of ammonium carbamate and an NH3/COn=2 equilibrium mixture to be:
TC=287"C,pc=25W2700 atm. To test the validity of this theory the predicted values for the
critical conditions were checked experimentally. In this process the knowledge of the phase behavi-
our on the NH3-COz plane was expanded to the NH&Oz= 2 value.
3.2. Experimental
Apparatus for visual determination of phase changes up to lo00 atm has already been discussed.25
The present investigation was made possible by the use of an autoclave which was recently developed
by researchers of the High Pressure Laboratory of Professor G. A. M. Diepen. A schematic drawing
of the autoclave system,44 suitable for visual measurements up to 2000 atm and 400°C,is presented
in Figure 5 . The samples (&50 mg) were prepared gas vol~metrically,~~ the maximum relative
error in composition being about 1-2"/, for NH3 and COz. The temperature was measured to
within 1 "C using a calibrated chromel-alumel thermocouple. Pressure was measured to within 2.5
atm using a deadweight gauge. The mixture was first kept at 160°C for 24 h to achieve equilibrium.
Thereafter, bubble-point measurements were performed in an increasing temperature sequence
up to the critical point and somewhat beyond, after which bubble-points were measured in a decreas-
ing temperature sequence. A smooth temperature-bubble-point pressure line shows that the
measurements are reproducible within experimental error.
Up to temperatures corresponding to the maximum bubble-point pressure, the bubble-point
pressure was measured at a given constant temperature by slowly reducing and increasing the
pressure until tiny gas bubbles appeared and disappeared. The maximum pressure point of the two
phase line on the pressure-temperature plane (point A in Figure 6) is referred to as the criconden-
bar;45 note that the cricondenbar need not necessarily occur on the bubble-point segment of the
two phase line. At molar NH3/C02 ratios below about 2.5 and, in particular below about 3.2,
the bubblepoint pressure line reached a maximum and thereafter fell very sharply with increasing
temperature.24~25 In this area the experimental technique became very inaccurate, particularly in
determining the critical conditions. Therefore a different technique was developed. It should be
noted that in the very high pressure areas investigated, which included the critical area, very unusual
phase equilibria can and did occur. In addition to the texts on phase equilibria already mentioned,4#
the reader is referred to studies such as those of R o ~ l i n s o nWichterle,46
,~~ and Hougen et aI.47c
for lucid discussions of high pressure phase equilibria.
Using the dead-weight gauge to achieve a constant pressure the temperature was varied very
slowly (about 0.01"C min-1, to avoid hysteresis effects) over the range f-P (see Figure 6) in which
f refers to the homogeneous fluid phase and P to the phase region in which 'liquid' (dense) and
'gas' (the less dense) phase coexist. As used in this paper the term fluid refers to a hot, highly
compressed mixture above its critical temperature and pressure. The change from the gaseous state
to the liquid state via the fluid phase is continuous, and therefore the fluid phase cannot be precisely
 71 yz2
II

23
Figare 5. Schematic drawing of the high pressure autoclave apparatus. I : Staff actuating magnets for mixing. 2: Closing nut (Inconel). 3: Copper ring. 4: Sample (contained
in IS). 5 : Glass covered iron stirrer. 6: Microscope (for viewing. 7: Nut for window. 8: Sapphire window. 9: Autoclave (Inconel). 10: Stainless steel holder for glass container
IS. 11: Lens closure. 12: Thermocouple well. 13: Lamp. 14: Magnets. 15: Glass container (filled with and submerged in mercury) with sample 4 in top. 16: Silicone oil.
17: Staff to adjust level of 10 (thus IS). 18: Silicone oil-hydraulic oil separator. 19: (grey) mercury. 20: Hydraulic pump. 21: Hydraulic oil. 22: Dead-weight pressure gauge.
23 : Pressure intensifier (see reference 45a).
Phase equilibria in ammonia-carbon dioxide systems 95

Figure 6. Schematic pressure-temperature figure for

a mixture of constant component concentration.
The solid and dashed lines refer to the bubble- and
dew-point lines, respectively. The letters A, B and C
--t
E
.3
I
>
6c4'
- 5 /
/
3'
3'

4
refer to the cricondenbar, the cricondentherm and
the critical point, respectively and I, g and f refer to
the liquid, gas and fluid phases. P is a two phase //
region.
Temperature -
defined. For example, working along the constant pressure line 1-2 (Figure 6) the temperature was
slowly reduced until at point 1' gas bubbles appeared, the meniscus appearing at the top of the
container (part 15 in Figure 5 ) as the bubbles rose; thus this point 1' is a bubble-point. Note that in
this area reduction of the temperature led to vaporisation (boiling) of the 'liquid'. Such seemingly
strange behaviour is common for multi-component mixtures near critical conditions and is known
as retrograde behaviour of the second kind.45 After reducing the pressure to another constant value
in the fluid area the temperature was again slowly reduced, along line 3-4 for example. At 3'
liquid droplets condensed along the side of the container (i.e. from the surface of the mercury) from
the falling 'liquid'; thus point 3' is a dew-point. By successively diminishing the pressure interval
between bubble-point and dew-point values the critical pressure could be localised within any degree
of accuracy within the experimental error. If the constant pressure line through the critical point C
was followed (line 5 4 , then as C was passed the homogeneous condition disappeared and a com-
pletely flat meniscus appeared abruptly at the exact centre of the sample's volume; with decreasing
temperature the meniscus rose disappearing at the top of the container at point 6'. By increasing

.'
2000
I I'
I
I

-E
0
I

P I200

I800
6 O i

400
O
t
140
L _J
300
Temperature ("C)

Figure 7. Pressure-temperature bubble- and critical-point values for mixtures of constant component concentra-
tion. The plots labelled a-g refer to mixtures of 66.4.67.0, 68.4, 69.0, 70.8, 72.1 and 75.0 mo1-X ammonia, respec-
tively. (For clarity the values and line for 73.3 % have been omitted.) The symbol 0 refers to the critical point, the
dashed line to extrapolated bubble-point values. All sympols refer to measured points (except for the critical points,
which were localised between bubble- and dew-points; see Figure 8).
96 S. M. Lemkowitz et ul.

the temperature from 6' to 5' (C) the reverse of the above mentioned behaviour occurred. All of
these phenomena were indeed found experimentally. Beautiful colour and extraordinary optical
phenomena, the so-called critical opalescence effects,42b also accompanied these measurements.
Since the exact determination of the critical pressure was extremely time-consuming and tedious,
the authors usually located this value to within 10-20 atm; the critical temperature could be more
easily accurately measured, namely to within 1"C.

4. Results and discussion

In total eight different mixtures of constant NHJ/COZratio (H20/C02= 0) were investigated, the
bubble-points, critical-points and, in some cases, the densities and dew-points being measured.
Up to mixtures of 32 mol-"/, COZ (component basis) all of the measurements were completely
reproducible to within the experimental error, even though temperatures as high as 275°C had
been reached and total measurement times of 2 weeks had elapsed. At COa concentrations of above
32 %, however, it was found that the bubble-point measurements were completely reproducible
only until about 250°C. Thereafter, and particularly above about 270-280°C, the phase measure-
ments were no longer stable, the mixtures becoming systematically less volatile with time. The

I I I I
30 265 270 275 280
Temperature ("Cl
Figure 8. The graphs labelled a-f refer to mixtures of 66.4, 67.0, 68.4, 69.0, 70.8 and 72.1 mol-% ammonia,
respectively. All points are measured points. The open symbols refer to bubble-points. the closed symbols to dew-
points. The critical-point is localised along that part of the two-phase line located between the two closest bubble-
and dew-points.
Phase equilibria in ammonia-carbon dioxide systems 91

effect was slow. For example, for a 33 mol-% COZmixture the temperature values of the bubble-
point line at about 260°C and 280"C, both at 1950 atm (see D and F of Figure 7) changed at the
approximate rate of $ 2 to 3°Cday-'. The critical temperature also changed roughly at this rate.
The change in the critical pressure was much more difficult to measure, but the critical pressure
definitely increased with time. For example, in the 2 days which were spent in measuring and re-
measuring the critical points of a 33.0 and 33.6 mol-% COz mixture it was found that the critical
pressure gradually increased by approximately 200 atm. I n order to minimise these time-induced
errors the phase measurements of the two mixtures with COz compositions more than 32 mol-"/,
were, above 250°C, carried out without interruption within an 8 h period. The values presented in
Figure 7 and used in the rest of this paper refer to measurements performed in this way. Figure 8
presents a detailed view of the phase measurements at and near the critical point.
The cause of this decrease in volatility with time for COz-rich mixtures at high temperatures is
probably the decomposition of urea. Via these decomposition reactions (formation of isocyanic
acid, biuret and triazines) free ammonia is formed. This free ammonia immediately reacts with the
free carbon dioxide present, which is the most volatile constituent contained in the mixture, lowering
its concentration and thus reducing vapour pressure of the mixture. Such behaviour has been
previously observed in urea-rich mixtures at high temperatures and low ammonia partial
pressure~.~5, 28
As already mentioned, it was found that as the NHs/COz ratio decreased the critical pressure
occurred at increasingly lower values than the maximum bubble-point pressure. Indeed, at NH3/

2400 1'"
2000

1600
-E
-
0
I

9
IM O

800

400

0 1 I I , I I
70 00 90 100
M o l % NH3

Figure 9. Temperature-pressure-composition projection for the critical and related values. The closed symbols
refer to the critical values. The open circles refer to the measured maximum bubble-point pressure and the open
triangles to the temperature corresponding to this maximum pressure. For mixtures of 66.4 and 67.0 mo1-X
ammonia the maximum bubble-point measurements were too high to measure and have been estimated (see
Figure 7). The vertical bars refer to the approximate uncertainty of this extrapolation. The vertical line deliniates
the 'ammonium carbamate' mixture, i.e. NHs/COe=Z.
98 S. M. Lemkowitz d al.

C 0 2 = 2 this pressure difference was estimated to be well over 800 atm. At these low NH3/C02
ratios (NH3/C02a2) it was also found that the critical temperature also occurred at a slightly
lower value than the maximum temperature of the bubble-point line. The maximum temperature
of the two phase line on the pressure-temperature plane (point B of Figure 6) is referred to as the
cricondentherm;*6 note that the cricondentherm need not necessarily occur on the dew-point
segment of the two phase line. While such seemingly strange phase behaviour at and near the critical
point is not unusual for multicomponent mixtures in this area, the authors nevertheless found it
striking that over a temperature range of just a few degrees the vapour pressure of the liquid phase
fell so precipitously and that there was such a large difference between the cricondenbar and critical
pressure. It is interesting to consider possible chemical reactions accompanying such behaviour,
but unfortunately the experimental method used does not permit the analysis of the chemical
constituents present.
From the eight mixtures studied the critical temperatures and pressures are plotted in Figure 9 as a
function of gross (component) NH3 concentration. From Figure 9 the critical conditions of an
NH3/C02=2 mixtures can be estimated to be: Tc=276f 1°C; p c = 1250k 10 atm; the critical
density was estimated to be 0.68f0.05 g cm-3 (Figure 10). Agreement with Kucheryavyi et aP9
( TC=287"C,p c = 2600 atm) is reasonable with respect to temperature but very poor with respect to
pressure.

d/iL
Figure 10. Critical density values as a function of
E 0.4 composition. 0 , Measured critical densities; x ,
0"
AC
known critical density of a~nrnonia;~sand +, critical
density of an NHs/COz= 2 mixture found by extra-
O" 60 10 80 90 I00 polation. Estimated value presented by reference 39.

Mol % NH3

What can be the cause of the poor agreement with Kucheryavyi et al.? In Figure 9 the maximum
pubble-point pressure and the temperature corresponding to this maximum bubble-point pressure
are also plotted as a function of gross NHs concentration. It is seen that at NHa/C02=2 a maxi-
mum bubble-point pressure of approximately 2350 atm and a temperature corresponding to this
pressure of approximately 286°C can be estimated, values which, of course, agree much better
with those calculated by the Soviet researchers. It is also t o be noted from Figure 9 that from 100%
t o about 74 mol-% NH3 the maximum bubble-point pressure and the temperature corresponding
with the maximum bubble-point pressure coincide with the critical point. it is just in this range that
Kucheryavyi et a/.39 used the previously published26 critical pressure and temperature values and
extrapolated them to NH3/C02 = 2 using the method of Joffe. This extrapolation is unacceptable
and accounts for the large pressure and small temperature error.
It is also seen from Figure 10 that the critical density value for a NHs/C02=4 mixture used
by Kucheryavyi et a/.38 in his calculations (pc=0.698 g cm-3) does not agree well with the
experimentally determined value ( p c = 0.60 g cm-3) presented here.
Furthermore, reasoning from the theory of Kucheryavyi et aI.,3e in which it is postulated that as
critical conditions are attained urea and water react completely t o form ammonium carbamate
[reverse of equation (6)1, it is to be expected that the vapour pressure of the liquid phase will increase
continuously up to and including the critical point, sincc liquid ammonium carbamate is much more
volatile than urea and water. As described above, however, (Figure 6-S), the liquid vapour pressure
decreases precipitously as critical conditions are attained.
Phase equilibria in ammonia+arbon dioxide systems 99

On the basis of the difference between the theoretically calculated3*and experimentally measured
critical point values for an NH3/C02=2 mixture, the difference in the measured critical densities
for an NHs/C02=4 mixture, and deductions from the theoryg9 which are in disagreement with
the measured vapour pressures at and near the critical point, the authors believe that there
is sufficient evidence to seriously doubt the validity of the theory presented by Kucheryavyi et aI.39
regarding the conversion-temperature maximum and therefore still ascribe to the theory of Inoue
et eventually supplemented to include possible conversion-pressure effects due to the
approach t o critical conditions. It is obvious, however, that more work is necessary to elucidate
further this phenomenon, which is so important to the urea technology. Such research necessi-
tates the measurement of constituent concentrations as a function of component composition at
temperatures and pressures up to and including the critical areas.
From the phase measurements performed it is also possible to extend the knowledge of the
bubble-point lines up to the range NHs/C02=2 and p=2OOO atm. This is shown in Figure 11.
In order to present the complete NHs-COz plane, previous mea~urements~~, l6 (NHa/COz = 3)

9:
2ooc

1600

1200
g
-9
0

800

Figure 11. Pressure-composition values, at varying

temperature, of the bubble-point and critical lines.
400
Bubble-point measurements, numbers 1-9 refer to
140, 160, 180, 200, 210, 220, 230, 240 and 250"C,
respectively. - - - -, Represents the critical line;
-.-.-.- , is the locus of the minimum-pressure com-
positions, at varying temperature. 0 1
70 80 90 I00
Mol % NHx

are included in Figure 11. The steepness of the bubble-point lines on the COz-side of the pressure
minimum relative to the much less sharply sloped lines on the NHa-side is due to the relatively
poor solubility of CO2 in the liquid compared to NH3. This behaviour, a t lower temperatures, has
been discussed in the 26 as has the practical use of diagrams of this type.

5. Conclusions
A temperature-pressure-composition model, based on the theory of descriptive phase equilibria,
has been presented for the binary system ammonia-carbon dioxide (no urea present) which logically
includes all known phase equilibria relating to this system. The most characteristic element of this
binary system is the reaction of ammonia and carbon dioxide to form ammonium carbamate. The
formation of this product, which is much less volatile than its reactants, leads to a temperature
maximum at all pressures (and, correspondingly, to a pressure minimum at all temperatures).
100 S. M. Lemkowitz ct al.

Knowledge of this temperature maximum at high pressures i.e. the azeotropic condensation
conditions, is most important to the urea industry.
The bubble-points and critical-points on the NHs-CO2 section of the ternary NHFHaO-COz
system at chemical equilibrium (urea present) have now been measured from 100% to 66.4 mol-%,
NH3 encompassing a temperature-pressure area of from 140 to 280°C and 50 to 2000 atm. Beyond
this composition (more C02) and temperature range the system is no longer reversible. Characteris-
tic of the phase equilibria of mixtures of relatively high COZconcentration ( N H ~ / C 0 2 2 2 is ) the
occurrence of a precipitious drop in pressure from the maximum bubble-point to the critical-
pressure. The critical values measured for an NHa/C02=2 mixture differ significantly from those
calculated in the literature. The probable cause of this difference is that in reference 39 no allowance
is made for the difference between the maximum bubble-point and critical pressure, a difference
which becomes very large at NHs/C02 = 2.

Acknowledgements
The authors wish to thank Professor G. A. M. Diepen and his staff for their interest in our work
and for their help in using the facilities of the laboratory and Ir H. J. van der Kooi, Ir P. Verbrugg
and Dr W. Durisch for improving this text.

References
1. Zemansky, M. W. Heat and Thermodynamics McGraw-Hill, New York, 1957,4th edn, pp. 461-468.
2. Kaasenbrood, P. J. C.; Chermin, H. A. G. Proc. Fert. Sue. 1977, 167, a : Discussion.
3. ScheKer, F. E. C. Heterogeneous Equilibria in Unary and Binary Systems Waltman, Delft (The Netherlands),
1960 2nd edn, a: pp. 52-60; b: pp. 54-55; c: pp. 121-122; d: pp. 168-170; e: pp. 78-83.
4. Zernike, J. Chemical Phase Theory Kluwer, Deventer (The Netherlands), 1955, a: pp. 179-189; b: p. 184;
C: pp. 243-244; d: pp. 146-155.
5. Broers, J . N. (1974); Kretzers, L. M. (1949-1950); Bezemer, C. (1949) Internal Reports Department of Chemical
Technology, Delft University of Technology.
6. Gmelins Handbuch der Anorganischen Chemie, Verlag Chemie, Berlin, 1936,23, pp. 327-362.
7. Chao, G. T. Y. Urea, its Properties and Manyfacture Chao’s Institute, West Covina, California, 1967,
pp. 298-324.
8. Briggs, T. R.; Migrdichion, V. J. Phys. Chem. 1924,28, 1121.
9. Briggs, T. R.J. Chem. Educ 1943, 20, 484.
10. Egan, E. P.; Potts, J. E.; Potts, G. D. Ind. Eng. Chem. 1946, 38,454.
11. Bennett, R. N.; Ritchie, P. D. ; Roxburgh, D.; Thomson, J. Trans. Faraday Soc. 1953, 49, 925.
12. Joncich, M. J.; Solka, B. H.; Bower, J. E. J . Chenr. Educ. 1967, 44, 598.
13. Swets, H . Internal Report Department of Chemical Technology, Delft Univcrsity of Technology, 1973.
14. Ellkernova, G. D.; Leontieva, G. G. Khim. Promst. (Moscow) 1962, 10, 742; Chem. Abstr. 1963, 59, 8588d.
15. Briner, E. J. Chim. Phys. Phys-Chinr. Biol. 1906, 4, 267.
16. Frbjaques, M. Chim. Ind. (Paris) 1948, 60, 22.
17. JBnecke, E. Z. Elektrochem. 1929,35, 716.
18. Terres, E.; Behrens, H. Z. Phys. Chem. Abf. 1928, 139A, 6Y5.
19. Kaasenbrood, P. J. C. Polytech. Tijdschr. Ed. Procestechnick, March 29, 1968, 198.
20. Scheffer, F. E. C. Heterogeneous Equilibria in Dissociating Compounds PhD Dissertation, University of
Amsterdan, 1909, 37.
21. Kaasenbrood, P. J. C. Chem. React. Eng. Proc. Em. Symp. 4 1 , Pergamon Press, London, 1971, p. 371.
22. Kaasenbrood, P. J. C. Chem. Eng. World 1974,9, 161.
23. Lemkowitz, S. M.; van Erp, J. C.; van den Berg, P. J. Deut, Progr. Rep. 1978, 3, 83.
24. Lemkowitz, S. M.; de Cooker, M. G. R. T.; van den Berg, P. J. Suppleinenr to Proc. Fert. SOC.1972, 131,
containing written contributions comment of J. D. M. Verstegen (Dutch State Mines), pp. 22-23.
25. Lemkowitz, S. M.; de Cooker, M. G. R. T.; van den Berg, P. J. Pruc. Fert. SOC.1972, 131.
26. Lemkowitz, S. M.;Zuidam, J.; van den Berg, P. J. J. Appl. Chem. Biotechnol. 1972, 22, 727.
27. Broers, J.; Lemkowitz, S. M.; van den Berg, P. J. J . Appl. Chem. Biotechnol. 1975, 27, 769.
28. Lemkowitz, S. M.; Vet, E.; van den Berg, P. J. J. Appl. Chem. Biotcchnol. 1977,27, 335.
29. Buck, A.; Rathgeb, K. Helv. Chim. Acto 1975, 58, 81.
30. Kucheryavyi, V. 1.; Gorlovskii, D. M.;Koshcherenkov, N. N. J. Appl. Chem. USSR (Engl. trans].) 1972,
45, 70.
31. Lemkowitz, S. M.; Diepen, G. A. M.; van den Berg, P. J. J. Appl. Chem. Biotechnol. 1977, 27, 321.
32. Lemkowitz, S. M.;de Cooker, M. G. R. T.; van den Berg, P. J. J. Appl. Chem. Biotechnol. 1973, 23, 63.
Phase equilibda in ammonia-carbon dioxide system 101

33. Durisch, W. Experimentelle und Thermodynamische Uniersuchung des Siedegleichgewichts des Systems
COFHZO-NHS unter Harmstoffsynthesebedingungen PhD Thesis no. 6238, Swiss Federal Institute of Tech-
nology, Zurich, Switzerland, 1978.
34. Cavalotti, P.;Colombo, D; Carra, S. 6th h i . Congr. Chem. Eng. Equip. Des. Autom. Parer E5.2, CHISA,
Prague, 1978.
35. Mavrovic, I. Hydrocarbon Process 1972, 50 (4), 161.
36. Inoue, S.; Kanai, K.; Otsuka, E. Bull. Chem. SOC.Jpn. a: 1972,45, 1339; b: 1972,45, 1616.
37. Kucheryavyi, V. I.; Gorlovskii, D. M. SOC.Chem. fnd. (Engl. transl.) 1969,11,44.
38. Gorlovskii, D. M.; Gorbushenkow, V. A.; Kucheryavyi, V. I. J. Appl. Chem. 1972,45, 1596.
39. Kucheryavyi, V. I.; Gorlovskii, D. M.; Koshcherenkov, N. N. J. Appl. Chem. 1975, 48, 320.
40. Gorlovskii, D. M.; Kucheryavyi, V. 1. Sou. Chem. Ind. (Engl. transl.) 1976, 8 (I), 72.
41. Poulisse, H. N. J. Internal Report (analysis of reference 39), Department of Chemical Technology, 1976.
42. Rice, 0. K. Critical Phenomena In Thermodynamics and Ph-vsics of Matter (Rossini, F. D., Ed.) Princeton
University Press, Princeton, 1955 a: pp. 4 2 1 4 2 2 ; b: pp. 423424.
43. Reid, R. C.; Sherwood, T. K. The Properties of Cases andLiquids McGraw-Hill, New York, 1958, pp. 32-33.
44. Tsikilis, D. S. In Handbook of Techniques in High Pressure Research and Engineering (translated by A.
Bobrowsky), Plenum Press, New York, 1968 a: pp. 101-112.
45. Rowlinson, J. S. LiquidF ondLiquid Mixtures 1971, 2nd edn., Butterworths, London, pp. 196197.
46. Wichterle, I. Fluidphase Equilib. 1977, 1, 161.
47. Hougen, 0. A.; Watson, K. M.; Ragatz, R. A. Chemical Process Principles John Wiley and Sons, New York,
1954 a: Part 1. Material and Energy Balances, pp. 78-86; b: Part 1. Material and Eenergy Balances, pp. 276-
279; c: Part 2. Thermodynamics, pp. 931-937.
48. Din, F. Thermodynamic Functions of Gases (Din, F., Ed.) Vol. I, Butterworths, 1956, 89.