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Ammonia Properties
Ammonia Properties
Ammonia Properties
200
°C; #5 har for the pressure measurements. The errors in-
‘woduced in interpreting the drawing ere probably leee than
+£0.25% overall. This estimate is based on two separate inter-
pretation, with «two year lapse between, and several spot or
partial interpretations. A different investigator was wsed for
tach interpretation.
‘A modification of the apparatus used for the ammonia
work has been used by Professor Franck to make measure-
tents for water [95], ialudiag the same preseute range, but
extending to somewhat higher velues of temperature. Those
data are believed to be accurate to within 1% over their
range, and this may be a reasonable estimate for the accuracy
oftheir experimental measurements for ammonia.
4.11, Data Set 14
Volumetric messurements have been made by Lichtblau,
Bretton, and Dodge [96] at 50 °C intervals along isotherms
including 300 °C < T'< 450 °C. The pressure range includes
500 atm < P< 2500 stm. Only smoothed values of the com-
pressbility factor for each isotherm are reported. The ex:
perimental procedure included a constant volume apparatus
in which the peesure was transmitted tow deadweight gauge
via & transducer. It is apparent from the article that very
careful design and thermodynamic analyses had been used in
this work
The authors claim an absolute accuracy of about 0.9%. If
this claim were valid, then these measurements would extend
the region of quality data for ammonia to an important part,
of the thermodynamic surface. Unfortunately results of our
analyses are nol in accord with the authors claim of sccurscy.
We have found the dats to be inconsistent withthe very high
‘quality data of set 3 as well as with the data of sets 8 and 13,
‘The differences are systematic, withthe data set 14 values of
density consistently low. The deviations are in excess of
several percent. Deta sets 3 and 8 overlap date set 14 along,
21 900 °C. Date mt 19 orelaps dete oot 14 for
several isotherms at the higher values of pressure. To ascribe
the inconsistency to data eet 3, 8, and 13 isnot feasible, pa
ticulerly aftr the analysis for dataset 3 in section II, 4.2. We
therefore must conclude that the data of ect 18 are in error by
at least several percent over their entire range.
Itis unfortunate thatthe actual P.g,T data points taken in
Ais eaperimeut mete uot seposted in the publication, Ie ie
conceivable that the unsmoothed values could yield some ra
tionale for the inconsistency, and perhaps a bess for corre
The authors also report values for the compressibility fa
tor for the binary mixture contsining 81% smmonia end
19% nitrogen forthe P,T region of dataset 14
5. Other Data of Mostly Historical interest
‘hie section has included a discussion of the thermody:
namie data of importance for this corelation. The order of
the discussion indicates our estimate of the relative impor-
tance ofthe regions ofthe surface, Thus the discussion ofthe
data began in section 2 with the equstion of state for the
‘eoesisting phases of vapor and liquid. Next considered in sec-
tion 5 were calorimetric measurements, such as specific hests
tnd latent heats and the properties for the ideal gas state.
‘The Pye? data for the single phate rogion forthe gas
liquid phases was discussed last in section 4. An important
pat of the discussion was devoted to the establishment of ac-
‘curacy estimates forthe data. In most cases the estimates ob
tained are conservative that is, the estimates we propose for
the uncertainties in the data tend to be larger than those
given by the original authors
‘The following list includes date that are mainly of only
Iristorical interest. Also included are some Pia measure-
tents that apply to very limited regions adequetely covered
by other data. The order of presentation of the properties
that given in the previous sections,
5.1. Coexistence Data
Vapor Pressure: Bunsen [21], Faraday 52], Regnul (24,
Bincke [97], Bril 98), Davies 95}, Holst (100), Bure and
Roberton (01, al of which are discus in reference 4:
Bergstrom (103) reported mearuremente in the range fom
the triple point to 30°C, which have an aerege deviation
from the NBS date of 0.5%; Henning end Sock [13] made
‘meararements over the sume range and thoe heve an eter
tage deviation from the NBS values of 03%
Specific volime of satureted ligui: Faraday (104),
D’Andreet (105) oly (16), Lange and Hert [33], Usher
{h07}, Lange [16], Diteri f0} nd Keyes and Brownlee
ist)
Specific volume of satus
{002} and Berthoud [24
itical point: Dewar [28], Vincent and Chappins [110],
Gentnergiver [111] Jaequerod[112}, Scheffer [113], Ca
dora and Giay (14), Esreicher and Sehnert (118), Bes
‘thoud [37], Mathias [116), Postma (117].
Triple point: Ruff and Hecht [119} Bil (8, Flo (120),
Bergstrom [102,Eucken and Kerwt (7)
Deg psn Dunns [2] bared rion (121), Regul
{26} Jownni 122), Ladenburg [123 Lange {108 Dickerson
{124}, de Foreand (125), Gib (31), Bri [6], Davies [9],
Burre] and Robertson [101], Keyes and Brownlee [51].
sd vapor: Dieterii and Drews
5.2. Colorimetric Date
cat capacity: Gy of vapors Regneult [96, Wiedman (296)
[Nernst (31), Haber end Tamara [38}, Giacomini (127), C, of
vapor, Masson {128}, Cozin (129), ‘Wallner [130]. Muller
[131], Keate [132] Schoer [133], Schweiker [134], Perting-
ton and Cant [135], Dixon and Greenwood [13], Pertington
and Schilling [187], Budde [138], Voller {135}, Nerast (32)
. of saturated liquid, Drewes [140], Dieteriei [30], Beau
tnd Ennis [141}, Ludcking and Starr [142], Von Strombeck
[143], Keyes and Brownlee (67), Keyes and Babeock (144),
Babeock (145), Eucken and Karwat [78]: C, of saturated
vapor, Babcock [145].
Latent hea of vaporization: Regoaul [28], Von Strombeck
em Rel Det, Vol 7, No.8, 1978660
143], Bstreicher and Schnert [146], Franklin and Keauss
hia
Joule-Thomson coeficent: Wobes {148}
7 Date
Experimental P, qT. data for the single phase regions
hich are now mostly of historical interest include the work
cof Roth [149] and of Keyes [50]. Other data for which the
range is very limited and adequately covered by more recent
nembuteatents iuclude weesureneuts by Hele [190], Drow
lee, Babcock, and Keyes (151, 152], Bridgman [153], Diet
richson, Bircher, and O° Brien (154), Ditrichson, Orleman,
and Rubin [155], Moles and Batuecas (156l, and Moles and
Sencho [157] and Mayan [158]. References 154-157 are
mesturements of the normal density for ammonia vapor at
standard conditions. Reference 153 includes data along one
Iwoderm at 90 “C for the pressure range 1000 atm Sr %
12,000 atm, Reference 158 includes only data for thermal ex:
pansion and compressibility for the liquid. The text indicates
these were derived from P.o.T’ measurements taken in the
ange from ~20 °F << 120 °F and at prestures to 100,
rmospheres. Based on the limited description given, the quali-
ty of the messurements ae adjudged to be somewhat below
shove of references 92, 94, T8 whieh Include te range of
reference 158.
I, Thermodynamic Surface
Introduction
In this section we develop an analytic thermodynamic sur
face for ammonia and derive the relations for the thermo-
‘dynamic properties to be calculated from it. We aleo include
detailed comparisons between thermodynamic properties
calculated from the surface and the corresponding exper:
imental dats, The reference state forall properties is taken to
be the ideal gas at zero kelvin,
‘This section comtans six subsections. The derivation of
the surface and of the expressions used to calculate the vari-
ous thermodynamic properties are given in section 2. Section
onesies eal
the surface and experimental date. A discussion of physical
features including the validity ofthe thermodynamic surface
close tothe critical point ae given in section 4. Section 5 on-
alos eslmates (OF ime overall accuracy of the ealcalated
properties. A short summary of the results and some general
‘comments ate contained in setion 6.
tated from
2, The Derivation of the Thermodynamic
Surface
Tn thi ewction we isin the lect squares sense, sclected P,
@, Tdata schematically represented in figure 2 to an snalytic
equation of state. No mathematical constrains were imposed
3m, end only P eT data were used in the least
(except thatthe equation is consistent with the
eal gas in the limit of zero density). The equation is a 44
term double power series function oftempereture and de
L. HAAR AND J. §. GALLAGHER
mental accuracy nearly all the available P, o, T data as well
as 10 produce limited extrapolations (bated on thermody-
namic arguments) of the surface into important regions
where data are sparse. The range ofthe equation is bounded
a Jow values of temperature by he triple point temperature
(195.48 K) and the meting curve for the liquid, and et high
temperatures bythe iotherm at 750 K (hich is epproximate-
ly 5/3 the eritical temperature). The pressure renge extends
1 5000 bar.
‘This section includes four parts, The general relations are
piven i section 2.1. The derivation uf dhe eting curve fs
given in section 2.2. Certain features of the fitting process
concerning the selection of statistical weights are given in
section 23, Conditions and relations associated with phase
equilibria are discussed in section 2.4
2.1. General Relations
Following Keenan et al. {80} the Helmholtz free energy
function is represented as the sum of two term: th First is
the contribution from the equation of state: the second is @
function of temperature only and refers to the properties of
the ideal gas. Thus we write forthe Helmholtz free energy,
Me Die TD, o
where °(7) is the contribution of the ideal gas. We define,
Ala, PFRT{n e+. 7, @
andsince
Pre'adive,
qs (and (sel,
ProRT{I+e0+e'2 0/30), °
seth
Qe=OB:, (Ba)
‘where By isthe second virial coefficient
‘The form we choose for Qi given in section Ieq (14),
OTT ctw, @
where r= 500/T, T is the value of temperature in kelvins,
111,2883498, gis the density in g/em and Ris the gas cons
tant, Equation 3 for the pressure has been fitted in the least
squares sense to the experimental P, 0, Tdata. The results of
values for the constants wy lated fa table 6, By
ions of eg (1) we obtain fr the entropy,
So, T-—Rln e+ eQ-er 90/9 x14S4(N, o
the internal energy,
Ble, PHReP9 0 4E%N), o‘THERMODYNAMIC PROPERTIES OF AMMONIA
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the constant volume heat capacity,
Clo. T-RoPa°0/0P+C°
the emhalpy function,
Mg MATER Qe! e19 QI TEM,
the constant pressure heat capacity,
C0, THAR.
where,
om 4+e0+e8Q/9e- 18 W/97-e'x9°9/2720,
and
Bo1+2eQ+4e' 0/0 ute'9"Q/OK",
(6)
oo
thet capacity forthe strated Hi,
nc, % (2PM. dee ®
SBPlBeh | dT"
where Ps the vapor pressure ofthe liquid given by Eq (of
tection I and where Pis given by eqs (3,4).
[SE and Cy are the corresponding contributions obtained
from 4°
APC -ES-RTU“In 481807)
@
so fare,
de
BATT fe 4°) (00)
e
TEAM),
where G°—E3 is given by eq 10 of section I. Equations (1-10)
are all that are required for calculating ll thermodynamic
properties forthe fluid. It is convenient for calculating prop>
fries of coenisting phases to use the explicit vapor pressure
versus tempersture equation, eq (I)of section Il As wil bei:
Justrated in section II, 3 the difference between calculations
sing the vapor preseure equation (lo abtain the anavieting
phates) and calculations using only eq (1) (with the usual eon-
ditions for phase equilibrium) is smaller than the uncertainty
assigned tothe experimental data
2.2. The Melting Curve
‘The low temperature Louudary of the erect
melting curve. The relationship between the pressure and
temperature of the melting solid was ealeulated by means of
the Clapyron equation, using th latent heat of fusion and the
specific volumes for the saturated lgu
for the latent heat the value reported by Over
Giauque discussed in section I, 3.3ds forthe specifi volume
for the solid at the normal melting point, we used the value
reported by MeKelvey and Taylor, discussed in section TI,
2b; forthe specific volume of the liquid we used the value
revorted by Cragoe and Harper. discusred in section I. 22a.
‘The Clapeyron equation isthe relat
48
oT
where the quantities ae as defined following eq (in section
M, except that wand w now refer tothe specific volumes of
the liauid and solid, respectively, and L refers to the latent
heat of fusion,
From the above data, the quantity =" =pxio
and eq (I) integrates to yield
a, ay
0=Bexp[sx10-4P-P)),
cr)
‘where 8, and P, are triple point values. (Bq (12) ignores the
small differences between the triple point values for the spe:
cifie volumes end latent heat and the corresponding values at
the normel melting point) Since P, atthe triple point is very
small the selatioushiy es be simplified wo
Phys Chem. Rel. Date, Vol.7, Na. 3, 1978662 L HAAR AND J. $. GALLAGHER
(6195.48 exp (10*Platm). a3)
Equation (18) is the relation we use to represent the coer:
isting phases of solid and liquid, which isthe low temperature
‘boundary for the corelation.
2.3. Stotistical Weights
‘The overing erierin ued forthe selection of weights
was the condition tha the derived thermodynamie wrfce
fare withthe daa within he accuracy eatimater signed in
section Tl For this purpose, the root mean squares of the
fractional deviation forthe vale of presure and deni
sore compared withthe szpenve experimental uncertain
tes for these quate, Weighs wee tsgned 2 ato yield
rma, vats which ate abou equal to the curacy asig
Tn sections I, 41 and T, 42, i was established tht the
“core® data shown in igre 4a of considerable higher ac
cacy than any ofthe other Pe T dala reported for
thot dscssed in section Hl, 42. Al other data have been
assigned relatively lw ststial weight, Dat that ovrap
these "core valet have been given sero weigh
Tom lcontensy ves ned in sson fi 42, betwen
the data of st 3 andthe data of st 2 near their region of
overap (The inonistency exits only forthe ochre cor-
Terponding to the lowe! slun of densi for dat et 3 an
seems to be largest at the higher values of temperature) In
consistencies of this nature could seriously compromise the
sccuracy of the derivatives of the thermodynamic surfac
even beyond the region of the inconsistency. To reduce the
effect of the inconsistency we adjusted the statistical weights
0.8 to smooth the transition between the two data rets, Thus
we eet to a6r0 the eatintcal weight for the
sponding to the lowest value of density for dataset 3 Simi
larly, we se the statistical weight to zero forthe isochore of
highest density of date set 2. The experimental values of den
sity for the next lowest density isochore of set 3 were adjusted
to split the difference between them and the results for the
trial surface derived in section Il, 4.2. Finally, the statistical
(for there adjucted data” woro reduced by
from those assigned to the main body of date set 3, In this
way a comparatively smooth surface has been achieved, but
atthe expense of some degradation in the fit to data set 2 at
the higher values of temperature in the region ofthe overlap
Excluded from the least squares fit were data that ex
tended closer tothe crtial point than the data of set 3, Data
thin ahout 20% ofthe critical density neat
the eriticl isotherm and to within 3% ofthe eritiel temper:
ature near the critical isochore, The data closer tothe critical
point were omitted, principally to remove a logial inconse:
teney associated with analytic thermodynamic surfaces
(These data also have certain questionable features; see rec:
tion TI, 46.) As was explained in section I, 2.1a, attempts to
reprecent the region close tothe critical point with an analyte
je equation can seriously compromise the representation not
only in the critical region but even in regions considerably
removed from the critial point. Thus all of dataset 9 was ex
cluded as were data associated with the values of the thermo
1.Phy. Chom. Re.
Vol.7.No. 3, 1978
dynamic parameters atthe critical point, Features ofthe ther
smodynamie surface near the critical point are di
section III,
‘The evteria for the last squares fit included tests for over-
fit, As we noted in section I, 2c, an analytic sueface that
yields the pressure within the accurecy of measurement
would yield an equation that seriously overfite the dencity
values in the compressed liquid region. On the other hand an
analytic equation that yields values of density within the ae
curacy of measurement would seriously overft values of pres
sure in the eritical region. We rejected equations of state that
produced such overfit.
2A. Coenisting Phases
The liquid~vapor saturation boundary is defined by the
Gibbs conditions for equilibrium between the coexisting
phases
rer, a3)
Preps, ay)
C=, as)
where the superscripts fg refer tothe liquid and gas phase,
respectively. isthe Gibbs funetion defined by
caatPie, 16)
Analytic representations for A(T) and Plg,7) are given by
eas (la)
‘The Gibbs condition for phase equilibrium was included
by a procedure that makes explicit ue in the least aquares fit
of values for the vapor pressure. In this procedure the Gibbs
conditions ate satsted only to within the accuracy assigned
Jn seetion II, 2.1 0 the vepor pressure dal,
employed ita follows:
Step A tral surface war derived by least
the P.,T data, without the Gibbs conditions
Step 2. The vapor pressure equation given by eq (I) of ec
tion Is used with the tial surface of step Ito ealelate trial
values for the densities of the coesisting phases. Thus we
solve
Plo TPT) ay
for values of density for the coexisting phases, where PLT) is
the vapor pressure equation and P(g,7)is the tral surface of
sep 1
Step 3. Using eqs (15,16) the Gibbs condition is written
Aloe, AUC
TT
e
as)
e
where ¢ and of are values for the liquid and vapor coex-
isting Jensties, enpectively, as calculated in sep 2. Thus P
is formulated in terms of the 4 parameters of the equation of
state (end the preliminary estimates for gt and gf)
Step 4. We now consider an expanded data set which in-
cludes the data used in step 1 plus values for the vaporTHERMODYNAMIC PROPERTIES OF AMMONIA 663
pressure, which for convenience have been included at 10 K
using eq (1) of section IL. A new thermodynamic
surface is then derived by least squares fit to the expanded
dataset. In the least squares fit we now include the dtterence
between the vapor pressure ‘“date” points and values for P
riven by eq (18)
‘Stop &. A-cacend sot of trial values of density for the coos
isting phates for the new surface is determined, using the
‘equation of state derived in step 4 and the vapor pressure
‘equation. Corresponding to these, the Gibbs energy condi-
tion eq (15) is then tested. In what follow, we shall use 4610
represent the small deviations from exact agreement.
Step 6. The dG values obtained instep 5, are now used to
stermine the very amall corrections to the vapor pressure
"data" required to achieve exact agreement for eg (15). This
done by Taylor series expansion. Retsining only the leed
terms in such an expansion we obtain the thermodynamic re
lation,
1
(E-3) eee, 09)
where Pin the mall coreton tothe vapor presare “ta”
Teed tatty the Gibs condone 5 eae.
Step 1, The final values for coring dense ate then
deterbined eeoring to sep 2aning eosin I
crementd bythe AP ales bined in ep 8 andthe egos
tion of tae derived in step 4
the dimensiones quantity AC/RT aha
step 5 are listed in table 7. The maximum is less than 0.0006,
which value corresponds to less than 0.05% uncertainty in
pressure, In practice differences are negligible between
‘alues forthe thermodynamic properties obtained by the pro
cedure consistent with using steps I through 7 and the much
simpler procedure in which the procedure is terminated after
sep §. However, for theriendynamie consistency, the valine
for the coexisting phases in Appendix A were determined us-
ing steps 1 through 7
“Tate, Gibbs function esos
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3. Comparisons of Derived Properties
with Date
In this section the thermodynamic properties calculated
from the derived surface are compared with experimental
deta. Comparisons with P.@,T data including data for phase
‘syle ‘wompainon
calorimetri data in section 8.2 and with values reported for
the second virial coefficient in section 3.3.
‘ne inured in weet:
an.
T data, Including Phase Equilibrio
‘The comparisons are presented es fractional differences in
percent between the ealeated and experimental values of
density. The results are illustrated forthe fit vo Pa,T data in
figures Sa, 5b, and Se. It is important to appreciate thatthe
‘uncertainties associated with various P,g.T data sets differ
from each other by up to several orders of magnitude, Fur
‘thermore, measurement errors are largely systematic, 0 that
the low quality data are, in general, thermodynamicallyin-
‘onsiotent with the quality date nd with the de
face). Thus the closeness ofthe fit for the vstious Po,T dat
sets isnot the important eriterion. Rather, what is important
is that each dats set be represented within the accuracy
sesigned that set. In most part an examination of the Figures
show that ths criterion is satisfied
Deviation plots for the “core” data are shown in figure Se.
‘Thee very high quality data extend over the region ofthe
surface (ge figure 4) that isthe most important technologi
cally.
In section I, 23 the small inconsistency ofthe data of set
3 in the region of overlap with the data of set 2 was resolved
by a small compromine i the fit for data set 2 and a some-
what greater compromise forthe fit to dataset 3. The devia
tion plots forthe suspect data pointe of et 3 are indicated in
Figure Sa (ond figure 4) by the citeles. The amount of the in-
‘consistency approaches 0.2%, withthe largest degradations
‘occurring at the higher values of temperature.
tis noteworthy thatthe one data point of data set 3 with
the largest fractional deviation (ymbol Zon the Figure) isnot
an outlier. This data point is very close tothe eriteal point
parts in 10,000. Infact, s can be seen in figure 4 the data of
1 Sinclude a numberof data points tha extend close tothe
critical point. The thermodynamic surface was able to fit all
ofthese data within the accuracy of measurement, tht is to
vrithin several parts in 10,000, as was the cate for the large
rajorty of the datapoints forthe data of sets Ito 4.
"The somperion shown in igure Sh and Be tand to mush
larger deviations than those forthe core data. Thus, forthe
data set 6, the deviation plot indicates these data are in
consistent with the core dats of sets 3 and 4 by about 0.4%
‘The very large differences shown for dataset 7aceur near the
al point, where these data are inconsistent with those of.
set 3. The largest differences forthe data of set 8 oceur
for the lowest icotherm at 473 K for the loweet densitie. In
this region the data are clearly inconsistent with the data of
set Sand withthe data of set 2. Except for that isotherm, the
fgreement with the data of set 3 in the region of overlap in
‘most parti within about 14%
{Lys Chem Ral. Dat,Vl.7,Ne. 3, 1978664 L HAAR AND 3.
Data set 1
4a
7 ae A
aa Presa, bat
Data set 2
+2
0
=
4
Data set 4 (Saturated liquid)
+3
0
-al on 03 10
Pressure,
Data set § (Saturated vapor)
‘hermodyoumicsuroce and ie eperineml dtl igure are pote
"core data For eons givens veces 1,2 apd 8 the
trae thet he hermdynami rae consent withthe POT
Data set 9 includes measurements made very close to the
critical point. These date were nol included in the least,
squares fit forthe reasons given in sections 1, 2.la and HI],
23, It so happens, st noted in section Il, 4.6, that these di
‘lso exhibit large thermodynamic inconsistencies. However,
the vory large deviation shown in figure Sb for thece dat
primarily due to the inadequacy of the derived thermody
humic surface as a representation of data very close to the
critical point. (A discussion of the fit fr the critical region,
‘J.Phye. Chom. Rel Dat, Vol, 7,No, 9, 1978
8. GALLAGHER
0} — ent panning giana ten ws wey ae FF
Pressure, bor
Pe a np ee teeter
30
sapere gre Sincere very bgh uly dat refered om
te ere ot ted in he derivation, Encephale gre,
tin tbe acorary signed them inet
including the critical region boundary, is given in sections
Mi, 4.1 and 1,42)
‘The largest deviations for dataset 13 (e fig. Se) occur for
‘the isotherm st 298 Kin the region of overlap withthe data of
sets Tand 10, The deviations forthe data of sets 11 and 12in-
dicate that thove data are inconsistent with each other and
with the data of set 18. Inconsistencies are even more ap-
paren for the data of set 14. These date are inconsistent wi
the data of sete 3,8, 13.THERMODYNAMIC PROPERTIES OF AMMONIA 665
Data set 6
490
= 90 Pressure, bar
=
3
4d Data set 8
2a
Soe cter, © fee
0 ser 7000 rr
Press
-20)
+5) .
Data set 9 eee ee
a at : a° ee ee 120
° + Pressure, bar
3.2. Comparisons with Calorimetrie Dato
‘The calorimetsie data included inthe comparisons are the
‘measurements for the coexisting phases and for the super
heated vapor, discusted in sections Il, 3.3 and II, 3.2, respec-
tively. The comparisons for the ovexning phases are shows
in figure 6. The comparisons for the superheated vapor sre
{given in figures 7 and 8. The calorimetric values calculated
fom the thermodynamic hhave been combined with
the contributions forthe ideal gas state, eqs (10) The values
for the ideal-gas state have been shown to be of very high se
curacy. section I. 4.
‘As we have stated in section J, 2.1d no ealorimetric data
used in the derivation of the thermodynamic surface, so
these comparisons are a severe test forthe derived 5
face
Figure 6 includes percentage deviation plots for calori-
metric properties for the coexisting phases, Included in the
fieure ate deviation nlts forthe Istent heat of vaporization
the heat capacity forthe saturated liquid, the heat capacity
{Lys Chem. Re. Dat, Vl. 7,No 2, 1978666. L HAAR AND J. 5. GALLAGHER
saat set 10
of mae age
i . : : 2 foe
0
Data set 1
+20] ° i
Press, br : cee
is : 7 eee uly . 2 . 30000
: +
-20
=
< Data set 12
ad :
3 cae Prasae bar ee
q eee ee
. pee TS
Data set 13
“20
: pres
tees
7 elec
Te, >
“20
Data set 14
20
Presse, bar
° 1090 apo
2.0) = zs . 3
oi Se, Secapton for gue Se
for the saturated vapor, and the heat capacity of the liquid at
‘constant presure equel tothe saturation pressure.
‘The experimental values forthe latent hea of vaporization
re those discussed in section Il, 3.38, and have been as
signed an overall aouracy of about 01%. The ealelat
values were obtained from the equation
LT HQs.T- He!.2) 2)
4LPhys. Chem. Ra.
Vol.7, No.3, 1978
‘The deviation for the latent heat are shown in the fist curve
‘on figure 6. The maximum deviation is less than 0.2%, which
‘occurs at the lowest value of temperature. The average of the
bsolute deviations ie lees than 0.1%.
‘The experimental valuee forthe hest capacity ofthe satu
rated liquid are discussed in section II, 3.3b. These date are
believed to he accurate to within about 0.2%, The ealeulated
values were obtained using eq (9 (with eq (1) of section Il forTHERMODYNAMIC PROPERTIES OF AMMONIA 667
+0 1
{LATENT HEAT OF VAPORIZATION
Bhan
AL a
DeVATIONS (96)
Sore
TEMPERATURE (*¢)
PURE 6 Clrimeti omparons fe the coesiting pases. The percent
‘elton are ped eran temperature forthe lect het, the heat
‘pec for the strated gba apc fhe nataated operand
‘hehe! eapaciy at eontnt presto the started giao seen
IL, 32 The mort important fer ie hat the eelted rales agree
ith enpernent amen to ihn the arercy of te experimental mee
“erent eacepl avalos of temperature sow about ~20 "for which
the pay of POT date has compromised the accuracy ofthe derived
sre,
aepep te
CURE 1. Calorie compares for sopeheted vapor. The perent
‘deviation vera pesre Between th aur auld fom the derived
Uhermodynanie sufoce andthe experimental date se section MI, 33,
‘Te fete of ot tha the average dria lean 035, ih
‘he meine than 1% occuring 0°C er satration, in ego
lor ich the Tate are ose
q Se
é =
——
ce
7 oe
a __—_— we
$
a
——— wwe
| «
~— ve
Pune 8. Deviation plots betneen ves of G, alee
‘meena nef un ar Ted be a seston
fret illerences ae plated vera press others 30°C i
Teale forts of temperature nthe ange O° 1300. la ely
‘cate the agrerment within the uncertainty aie or the ihe
Salen af empertre athe higher vrs of pes: Noe tha he
Tower valaesof temperate he pure iced eins of he sac ey
ear tothe strated ape sales In thee reo the contain
{fom he thermodynani rac ger than ha ofthe eal a
jon between the calculated and the
experimental values ie about 1.0%, and this occurs at the
lowest value of temperature. The average of the absolute
deviations is less than 04%. For values of temperature
greater than ~20 °C the maximum deviation does not exceed
04%.
‘There arene di
the saturated vapor. The values diseuseed in section Il, 33a
‘were calculated from the equation
raciso-2.
crecio.
an
where Ci and L are measured quantities. Because equation
21) involvee the differentiation of the latent heat and in
volves a difference between large numbers, we assigned the
comparatively large uncertainty of 1.5% to these data. The
values calculated from the thermodynamic surface were de-
termined from eq (9). The figure shows a monotone decrease
1.Phps Cham. Ral. Date Vol. 7.No. 8, 1978668.
in the fractional differences for C¥ ass function of
temperature. The largest deviation, about 2.0%, occure at the
lowest value of temperature. For values of temperature great
ferthan 0°C the deviations do not exceed 1.0%
Experimental values for G, forthe saturated liquid are dis-
cussed in section II, 8.8b. The ealeulated values are derived
fiom the thetmodysenie sunface using eg Os). The constant
pressure heat capacities are very nearly equal tothe corre
sponding C, values, Thue the deviation plot forthe C follows
the trend forthe C, values, except thatthe magnitude of the
eviations ae slightly smaller.
‘The most important conchision from figure 6 is thet, ex
cept at low values of temperature where thee is « paucity of
ccurate experimental Pig T data for the single pase
regions the calorimetric values calculated from the surface
are in accord with the experimental data for the coexisting
phases almost to within the accuracy of measurement
Figure Tis comparison between calculated and measured
values for the heat capacity ofthe dilute vapor. The exper
rental valves are diteuseed in section TI, 82. 1 was noted
‘Heri tha Ue angen utee uf eto i these easurenicnts
is from the random seater of the data, approximately 0.2%.
‘The caleulated values have been obtained using eq (8). The
ordinate inthe figure is the percent fractional difference and
the abcissa the pressure in har. The straight line segments
join the individual points. Bach line includes points near (o
within degree) the value of temperature designated inthe
Tiguc. In cues where several dt
together, the ndvidcal deviations were averaged. The max
imum deviation approaches 1% and this our cle 10 the
saluted vapor sate a OC. The average of he magnitude
At the deviations isles than 039%
Figure is ery similar o figure 3, In tha igure the same
calorimetric data are compared with values calelated forthe
nd see section I, 1. The net signin
comparison vith figure 3 is the ietene i the maximum
devintion, However, except fr one orto pint the map
tudes of the deviations are about the same, Pariclrl for
telus oftemperture above 35°C the compan indvates
‘ery small degradation ofthe accuracy of he derived surface
4. ”
Figure Bisa comparison of the C values given in table Sof
section Tl and those calulted from the thermodynamics
fee. The fractional differences are plated a function
pressure in bars forthe values of temperature OF < «300°
“The presue ange extends, atthe lw value of temperature,
Aerner the coturaed vapor sate and atthe higher alee
temperature. to 125 bare. The principal featre of the com
parison is that over most of the range the deviations are less
‘than several tenths percent. The notable exceptions are atthe
highest values of pressure forthe isotherms at 250° and 300
C, where the large deviations, approaching 2% at 300 °C
and 125 bar, are direct consequence of the procedure we
sets 2 and 3; see sections Il, 42; IM, 23; IM, 3.1, This com:
promise is preferable to the situstion that would have ob:
‘ined if the small inconsistency had nor been smocthed. For
then the degradation in the C, values would not only have
1. Phys: Chem, Rel-Dete, Vo. 7, Ho 2, 1978
LL. HAAR AND J. S. GALLAGHER
been larger, but would have extended over much large re-
ions ofthe surface,
3.8. The Second Viriol CooHficiont
Figure 9 includes comparisons ofthe second viral coef
late from oa) Galld curve) with value repo
‘ed by Hirschfelder et a. [159] (circled point) and Rowlinson
[160] and Keyes (161) oxed points. For values of tempera
than 423 K the agreement is ner within £1
atthe lower values of temperature the results of
Rowlinson tend to be lower. At 273 K Rowlinson’s value is
shout 40 em?/mol lower than the vale ealulaed from eq
(Gx) and about 30 em?/mal lower than the value obtained by
Hieschfeder et
‘The ress reported by Hirschfelder etal were derived
from the data of Myers and Jessup, data set 1, using a
taphical method. This involved an extrapolation to 2er0
resware of the volume resduslsesleulated from the dat for
‘ach isotherm, We have established in chapter Il section 41,
thatthe date of Myero and Jesup are accurate almost to
within their seater, that to about #0038, I we apply thi
uncertainty tothe volume residuals used in the graphical
analysis, we obtain an uncertainty of about Sem” ma forthe
‘xtrapolation for the isotherm at ¢=100 °C, The uncertainty
for the extrapolations at lower values of temperature is a
leat thi large Is apparent fom the igure therefore, that
the reeulte of HireeMalder otal rein accord with values
Calelated from eq () within the accuracy of the graphs!
analysis by Hirschfelder et al
‘The valucs listed by Rowlinson were calculated fom an
equation derived by Keyes [161] several years prior to the
work of Hirschfelder et. Though details were not given it
appears that the derivation i based on a least squares teat
creme of volume residuals [168 for
PT data of sts | and 2. Shorlly thereafter, Sockmayer
{163 16] used those B, values im his approximation forthe
Stockmayer potential for ammonia, Then, subsequent t the
Hirschfelder work, Rowlinson (160), Based in part om unre:
ported experiments at his laboratory, selected the results of
Keyes for his further development ofthe Stockmayerpoten-
° he Blocknayer potent
rmonia obtained by Rowlineon is recommended in the refer
cence work by Hirschfelder eta [165
Even though there appears to have been a general consen-
sus in its favor, there is serious defeet in the Keyes treat
iment. We note that volume residuals forthe lower isotherms
Ihave a great deal of curvature a a function of pressure, par
ticularly inthe region near the eseniatemce bows aloo
‘90 degrees curvature for temperatures below 80°C), Thus the
values for B, calculated by Keyes are sensitive to his (arbi-
trary) choice for the pressure dependence fo the volume re
siduals. (Keyes ignores the fourth virial snd al virils higher
‘than the fifth, except that he includes the fourteenth in hie
representation of the volume residuals as a power series in
premure:) I eppear 1 us that large par of th diffcsmee
between the values for B; from Keyes and those ftom the
araphical analysis are due to the particular representation
used by Keyes.
‘As we have demonstrated, the results for By calculated‘THERMODYNAMIC PROPERTIES OF AMMONIA 669
-100-
7 700
[EUR 9, The eon vil uefiet vers tempertare see section My
SA The sll ne repent sles elated frm the thermody
orf The ced pointe ae tle repre by Miele et and
tHebosed pint we valerie by Keyer and Relies
from our thermodynamic surface are in excellent agreement
with the very accurate heat capacity measurements for the
dilute vapor. This ie strongly suggestive that our calclated
second virals are quite accurate. We note that with inereat-
ing values of temperature above the critical, the plots ofthe
fet, and the results obtained by Keyes and Hirschfelder are
in good accord with those values calculated from the thermo-
dynamic surface.
4A, Thermodynamic Symmetry ond the
Critical Region
Certain symmetry features ofthe thermodynamic surface
inthe eritcal region, including the critica iochore and the
al isotherm are discussed herein. The section contains
arts. Section 4.1 meiudes rome comments related 10
the extent of the critical region. In section 4.2 we discuss cer
tin features relating to thermodynamic symmetry in the
Vicinity af the evtial paint Camparicnne arr given with
results of critical sealing, Section 4.3 includes a disevsion of|
certain calorimetric symmetries.
4.1. The Critical Region
‘That the analytic surface was not coerced to be consistent
with experimental data inthe immediate vicinity ofthe erti-
cal point is an important feature of ths correlstion. As we
hhave already stated, sections I, 21
namie inconsistency must
and IIT, 2.3, «thermody,
I when an analytic surface is
coerced to fit such data. To verify this conclusion, we im>
posed on the analytic surface our best estimate for the
parameters of the critical point, the values given by eqs (1)
and (9) of section II. We also included in the least squares fit
{he thermoaynamie featares assorted with he dvergence
‘of the compressibility atthe critical point In this way we in
veatigated the de
funetion of how strongly it was coerced (ia
weights) to be consistent with our best estimates for the
values of the eritcal parameters for ammonia. As expected,
‘egradation did occur. The errore seemed to increase with in-
‘creasing satstical weights, that is with improvement inthe
realization by the surface of the critical point. The quality of|
the surface in those region of dataset 3 that lie closest tothe
cites! paint cocmed tn euffor the grestect degradation
However, the degradation extended to regions far removed
from the critical point. The errors were found to be largest
for the heat capacity valves. Even the very small amount of
coercion needed to produce only a 30% "improvement im
the Pa fit atthe crtiesl point caused serious degradation
in values for C, for the dilute vapor at low values of
tempereture. The devintions from experiment for this case
were found to be about 100% larger than those shown in
figure 8
‘We now illustrate the extent of the critical region. We de
fine the eriieal region a that region else to the critical,
point for which the derived surface would yield errors primar-
ily because the thermodynamic surface is analytic. The so
Tine in Figs If rapreuante the liquicevepar
{or the derived thermodynamic surface. The open point just
below the dome of the curve is our best estimate for the loca
sion ofthe critical point, eqs (1) and () of seetion I. It ies
about 1 K below the entical point ofthe (uncoerced) derived
surface. The symmetrical dashed curve above the dome en:
closes what we believe to be the critical region for our sur-
Anncity the dashed nye Hes
about 10 bars above the critical pressure and about 4K above
the eritical value of temperature. It intersects the dome at
values of density approximately 20% larger and 20% smaller
than the erieal density, corresponding toa value ot temper-
ature about 1.5 K below the value forthe ertieal point of the
derived surface. The solid points late those data of data set,
in the general neighborhood of the ertieal region. Several
of the date points le very close to the boundary one isin
side). All ofthe data shown in the figure are fit by the surface
to within their accuracy, that is to within several parts in
10.000 [eee section IIL, 31). A turther discussion ot the qual
ity ofthe it i given in section IIL 42, immediately following,
42, Tharmadynamis Symmatry andthe Critical Baglon
Tn this section we compare thermodynamic values caleu-
lated from the derived thermodynamic surface with predic:
tone of simple scaling [166]. The dached curve in igure 10
encloses region somewhat smaller than that usualy asoci-
ated withthe renge of validity of simple linear sealing. Sim
ple scaling has been used to represent thermodynamie prop-
tries along the erticalisochore out toa value of temperature
Phy. Chem Re, Dato, Vl.7.Ne. 3, 1978670
[eI 10, The dome fhe oenting phase satin IL, 1. The soit
"inn retain he sateton sates elelted (om the theme
{vace Toe ai aoe ate poof ota 8 et ee
‘ny ofthe eral pn. The open ce jt below the Top ofthe
(dome ict the "perimental yale forthe ere ot, sets
25. The dae carve js aoe the to fhe dome eacoer wat
Feed nthe tent abe real eon, To fee of ote ta he
‘hermodynani uface nace ih al the data pints Gli point)
te wshin the ecurcy af mesnurement nat he qulty of the tap
fears be compel neni tothe covets the eit pit
"Tn together nu cei etre of gues an 12 oppo hs he
thermodynamic ufc avatar representation or te Fepian eter
‘doth ere region
bout 3% higher then the value of the critical temperature,
tnd on the eitcal izotherm to a value of density #25% from
the critical value, Thus thee isa region ofoverlap where i is
believed simple sealing and the derived thermodynamic su.
face are both valid, except that the former uses the correct
‘values ofthe ertial parameters while the later does not. We
shall eompare the results of the two methods on the critical
jsochore and onthe critical isotherm.
‘The thermodynamic quantity we compare isthe isothermal
compressibility, The isothermal compressibility is defined by
-3@)
‘The inthermalsompoosiy em seve pre for the
thermodyoamie earface, Simple sealing ile, for esa
plerefeence 167)
k,
oxen, (2) eo
onthe ie hohe nd
okra Se es
‘on the critical isotherm,
Values for the “universal” exponents y and 6 have been
reported by Sengers etal. [167], based on a correlation in-
volving # number of substances. The constants A, and As; for
smmonia lio ware obtained from parameters for ammanis
2.Phy. Chom. Re. De
L. HAAR AND J. $, GALLAGHER
reported in reference 107. As we indicated In secton Th, 6,
the data available for ammonia in the immediate vicinity of
the ctitiesl point are questionable, Therefore, we are more
concerned with comparitons between the “universe!” con-
stants reported by Sengers etal. end those predicted by the
surface than in comparicons between the respective magni
tudes of Ky. To accomplish this, we compared values forthe
natural logarithm of @* Kr.
Figures 11 and 12 compare, on a logarithmic scale, results
calculated from our analytical surface with values caleula
from eqs (23) and (28), In those igure, the slid lines repre
sent values for @K; caleulated from the thermodynamic sur
face at very close intervals. There ino detectable waviness in
the curves connecting these points, and we conclude, there
fore, that the thermodynamic surlace yields smooth erva
tives, The results of sealing ate indicated by the dashed
straight lines. In figure 11 itis rather remarkable (likely coin
ial that the roclte for cealing ar
with those from the esleulated thermodynamic surface from
the critical region out to value ofthe reduced temperature
‘ear 0.1, The value forthe “universal” constant y obtained
from the thermodynamic surface is y=1.16. The value trom
reference 167 is y=1.19. This agreement is well within the
estimate for accuracy ofthe scaling result.
Figure IB llusratca significant differences
ison om the eriticaljotherm. First ofall, the thermodynamic
surface yields two different curves, corresponding to values of
density greater than or less than ertical. Now, except in
regions close to the eitical there are ample PT deta of very
high quality, as ustrated in figure 4 and the derived thers
modynamic surface is in very good accord with these quality
PresT data. I is apporent, thorefore, that simple ceaing om
the eriical isotherm results in serious oversimplifcation at
large values of the reduced density. It is interesting to note
that, as we approach the critical point, the values calevlated
from the analytic surface tend to small differences forthe two
branches. The two branches cross the resull for eitca seal
ing ata reduced density near 0.17.
‘We cannot obs
from the analytic surface an unambigu
‘ous result for the value of the constant 6. We have made
several estimates, fist we considered the region including the
values of reduced density from 0.19 to 0.30. The "best"
Straight lin that spits the diference between the results for
the two branches, ave 434.5. If we change the region slight-
ly so as to include reduced densities from 0.20 to 030, we ob-
tin obo. If'we conlder just tne region given by 0.19 3
0.21 we obtsin 24.7. The result from simple scaling is
3,
Me af simple erating an the
sritical isotherm tend to fail at values of density that differ
from the critical by more than 20%. The results for the ther
rmodynamie surface are in closest accord with those of sealing
near the critical region boundary illustrated in figure 1U. On
the critical isochore the agreement with scaling is within the
accuracy ofthe sealing result,
Ins a very interesting feature of figures 11 and 12 shat
‘over most of the region included in the figures the values
calculated from the thermodynamic surface lie on curves in
Aiainguishahle from steaight lines. Deviations occur only"WERMODYNAMIC PROPERTIES OF AMMONIA sr
(bar)
10
‘ane 1. The eompeniiliy om the etl nchores ae setin I, 62
"The recipes ofthe ithemal sempre ie pote vere the
reduced temperature T==T/T~ The soil line represent vauee
Calewned fe te thermodynamic surface, The dashed ugh line x
{hereof fnew ealing. Te eid ine wan eppronate ih ing
repreveiton oie vale cleused rm he herman re,
‘The gant the ale ofthe sles ofthe ight nes The featare
cf notes the eel! seco betwen the peision fine sealing
‘eo the rel point. The ale ef rece temperate gil 0)
{eat the boundary ofthe crea rein show in figure 0
se eritcal region and at very low values of density. (For the
ilute gas a straight line representation cannot apply.)
4.3. Colorimetric Features
In this section we describe certain qualitative features of
ne ealorimerric values eeleulatea ftom the thermodynamic
urface. Figures 13 and 13b contsin isobats of the heat
ty at constant pressure as a function of temperature.
“igure 18s inchudesisobars forthe pressure range 10< P<
igure 13b features a closer spacing of isobar for
vressure interval bracketing the eritcsl preseure, 50 < P<
50 bar. The vertical dashed lines atthe lower values of tem
verature connect the two values of Cp corresponding 10
iquid-vapor coexistence. There is a cross-over near 50 bar
velow which C, values forthe saturated liquid are larger and
bbove which they are larger for the saturated vapor. Another
feature ofthe figures isthe trend of the maxima toward high
+ values of temperature with increasing values of pressure
These trends are in acord with results for other Huids; see
ference 80 for water.
“The reciprocal of umes the
‘he maghtude ofthe reduced deny, leer The values eee
‘rom the Sheedy sulce frm to separate ances, th soll
‘hare. The we branches rd to oer acer with Screg value of
he redced density. The dated le ithe rer bined rom lear
scaling ith the au ofthe slop. The etre nt tt esis of
ie cannot be extended very ft rom he rip on the
5, Evaluation of the Thermodynamic Surface
In this section we obtain estimates for the accuracy for
values of calorimetric properties calculated from the thermo:
dynamic surface. The accuracy depends on the smoothness of
the surface, the quality ofthe fit to the Pj’ data, and the
thermodynamic consistency ofthe Po,T data. The uncertain
ties in ealeulated Gy values are appreciably larger than those
1.Phys: Chem. Rak Dot, Vol. 7, No.9, 1978m
‘omperature, K
um pears bet cope are plted versus vales of tompreas fr
avowsvaluen of restr, Ti gare nes mon of the ange he
Served thermolysis srr. The vereal dashed nes its the
‘Senin t gidsepor conser For aero preemie ee
than aout Sri wale forthe snared tu ages Bat
sovethn vale f rene, Calero hatred apr ae ihe.
for the eartespondine PT values: compare Resers SR
Therefore the very small uncertainty inthe ideal-gas values
in thie analysis can be ignored
‘As we explained in section I, 2.14, an important feature of
four approaen is that calorimeinic data have not Bee” Yn
‘eluded in the derivation of the thermodynamic surface. Its
this feature that enables us in section 5 to assign clos tl
cerances forthe accuracy of the ealenlaed ealorimettie prop
1.Phys-Chem Rel: Date, Vo. 7,o.3, 1978
L. HAAR AND J. S. GALLAGHER
vith those of
erties. Comparisons of results of this corre
other correlations are given in section 5.2.
5.1. Accuracy Estimetes for Cand H
‘We first consider the accuracy forthe region covered by
Ue ve1y high quality “core” date shown schematically in
figure 4, In sections Il, 42 and III, 3.1, 3.2 those data were
shown tobe of uniform quality and in aceord with each other
and with the thermodynamic surface, In other words, these
data (and the region ofthe thermodynamic surface scheme
ically lustrated in igure 4) are of uniform thermodynamic
consisteney and accuracy (excep! in small region of overlap
fof data sete 2 and 9 and except for values of density forthe
saturated vapor). Tie feature greatly simplifies the analysis.
‘We note that different parts ofthe surface are more sen
sitive to measurement error of a given fractional size than are
‘others. Thus calorimetric values ealeulated from the derived
thermodynamic surface will vary in accuracy, even though
the quality of the PT deta end the fit to them of the
derived surface are uniform In particular, fr egions of the
thermodynamic surface where the Pgisotherms tend to very
large curvature or are very lat or very seep compared to a
reference region, we would expect some degradation from the
sceuracy achieved in the reference region. We take as refer
tence those regions for which the very accurate calorimetric
data exist. Thus for the gas phase the reference region isthe
dilate vapor for the liquid, isthe satorated guid stats.
‘A useful thermodynamic function with which to quantize
this intuitive analysis is the isothermal compressibili
defined by eq (22) We see in figures 6 and 7 that, except
where the P,o.T data for the single phase regions are very
parse or nonexistent, the values of Cy caleulated from the
thermodynamic surface agree withthe experimental data (0
thin 01190: Though she accursey af the caleulted values
(our reference values) do not appear to be sensitive to the
isothermal compressibility, there is @ trend in figure 710 in
creased degradation with increased compressibility It is seen
in the figure that along an isober the factional error tends to
decrease monotonically with increasing values of tempers-
ture, and so does the value of the isothermal compressibility.
in accuracy from this comparison is appreciably less that
linear. We assume, therefore, that linsr degradation with
isothermal compressibility forthe calculated C, values yields
seonservative estimate forthe gas phase. Based on this ana:
(2/2) arane. 0
where (8Cy/C,P is the fractional uncertainty in Cy that we
Wish o estimate andthe quantity (6C,/CyPny is the reference
value of uncertainty, given by
(86,6 Pry =0.008, 26)
ig the feothermal eamprescihility unltated a the pint ofTHERMODYNAMIC PROPERTIES OF AMMONIA ora
1nd K," is the analogous reference value. For con-
venience, ths reference is taken as the velue for th ideal gas,
KseUP. @
We use eqs (25-27) 10 calculate unce
of density in the range @You might also like