THERMODYNAMIC P OPERTIES OF CHLOROFBR

D.N., VISWANATH,D. S.
B Y SESHADKI, A N D KULOOR,N. R.
India)
(Depnrrnlenl o f Cilernical Enzineering, h d i m Inrrilurr o f Science, Ban&we-I2,
[Received: January 30, i968J

Thermodynamic properties of chloroiorm have been evaluated up to a

tcmperature of 750°K and a pizssure o f 200 atmospheres, using Martin and
Hou cquation of state. Tables of thermodynamic properties and a temperature
entropy diagram are presented.

(1) MoIecu!ar Weight a n d Cririral C o n s t a m s :

The data on thc critical constants of chloroForm deterinined bv verioirs
investigators are presented in Table-1.

Moiecirlirr veigkr w d criticnl cunsranrs o;ci~ioro,'orm

Molecular weight of chloloform-119.39
Year Investigltor T,.^IC h,a m . p,$c,c. Method Reference

1878 Sajotchewsky 533.16 54.9

1895 PIctet and Altschul 531.96 ....
1902 Kuznen and Robson 535.06 53.8
I923 Her2 and Neukirch 535.66 ......
1934 Hitrand 536.66 ......
1943 Fischer and Reichel 526.76 ......
Values selected 536 71 54.0
R - disappearance of the meniscus.
b -law of rectilinear diameter.
c -disappearance of the droplets after- the meniscus has broadened.

In the above table, t h e data prior ro 1900 are included for historical
Completeness only. Chloroform uscd by Kuenen and ~ o b s i i n "was prepared
from chloral and was carefully dried with calcian~chioride.
1 79
180 D.N.,
SF~ADR D. S .
~ , VISWANATR, AND N. X .
KULOOR,

Hers and ~ e u k i r c h ' have

~ riot stated the purity of chloroform used in
their investigation. Nowever,the accuracy of the temperature drierminations
is stated to be t 0 . 2 ' ~ .
Though E3nrandg, and Fischer and ~ e i c h z l ' did not state the purity of
the sample. they have done careful work. The value for the critical tonipera-
ture determined hy Narand, a d Fischer and Reichel agree very closely.
Hence the values are averaged and this value has been used for the present
inves:igatlon.
The criticai pressure and density are not known to a great degree of
accuracy. Hence the values were rounded off t o two sigzificant digiis and
\+ere used for this work.
2. Vupaur Pressura :
The vapour pressure of chloroform has been determined by various
investigators like Beckmann and ~iesche', Drucker e t a i 5 , Hcrz and ~athrnannl*,
Scatchard and ~ a ~ r n o n d Kuenen
s ~ ~ , and ~ o b s o n " , ~ e x " . and ~ c h r n i d t ' " ~ ~ .
~ t u l l ' has
~ made a critical compilation of the vapour pressure o f chloroform
up to the critical point. Data up to a temperature of 4 3 3 " are ~ available in
the hternational Critical ~ a b l e s ~ ! The available vapour pressure data along
with the range of availability are presented in Table-2.
Kuenen and ~ o b s o n 'dried
~ chtoroform carefully with caiciunl chloride,
but they were unable t o reduce the action of chloroform on mercury (which
takes piace a t high temperatures). They did not mention the accuracy of the
vapour pressure data. Beckmann and kiesche"have not irrntioned the
method of preparation of chloroform and the accuracy of their vapout
pressure determinations.
TABLE2
Voporirprcssvre of ehlnraform ---
Year Investigator Range of Range o f
temperature, OK pressure, atm. Ref'rence
-- .~ -. --
1902 Kumen and Robson 517.7- 536 2 47 7 - 54 6 12
1912 Herz and Rdihmann 300 2 - 334.2 0.29 - 1.0 11
1914 Beckmann and Liesche 291.2 - 343.2 0.2 - 1.4 1
1915 Drucker et al. 209.0 - 262 9 0.0 -0.04 5
1916 Rex 273.2 - 303.2 0.08 - 0.32 19
1921 Schmidt 293.2 - 373 2 0.22 - 3.2 22
1926 Schmidt 273.2 - 303.2 0.08 - 3.2 23
1928 International Critical
Tables 213.2 - 433.2 0.0 - 111.6 33
1938 Scatchard and Rayrnonds 308.2- 333.2 0.3 - 0.95 21
1847 Smll 215.0 - 536.2 0.0 - 54 27
-
 The vrpour pressure data of chloroforn~ determined by Drucker el
ocrca:n to pressuresup t o 0.04, a m Though the purity of the sample used is
not Pba errors in the pressure lxeasnrements are s t a t ~ dto be aroirn&!
G,;x'~ mm. Rowever, a s this work does not encompass such a Iow pressure,
:he data of Drucker et al. have not been used for this investipaticn.
ex" used the Mercfr A. R. quality chloroform. The sample was
fractionated, %henshaken w i t h concentrated sulfuric acid, and finally
u,ith distilled water, and dried. The accuracy o f the vapour pressure data is
:,ot presented.
3chmid12% 23 also did not state the purity of the chioreform used except

state that $he sample was subjected to carefol drying and frscrioaai distiila-
rion. The accliracy of the da:a is not mentioned.
~ ' not mention the purity of the sample
Scatchard a n d ~ a ~ m o n d sdid
csed. The errors in the measurement of pressure are slated to be Jess lban
C 05. nm.
For thi8 investigaiion all the available vapoui pressure data were
combined and smoothened. The smoothened vapoilr przssuie data h a ~ been
e
used for this investigation.
The vapour pressure data over a temperature range of' 275% t o 3 4 0 ' ~ ,
which covers a pressure range up t o "1.2 atmospheres, were fitted by the
method of least squares, to the equation :
log P - A + B , ! T + C ~ O ~ T + D T [:I
where A
B
-- -
- 29.593966
1025.8492
C - 14.831037
D -- E.47OZh61 x lo-' .
'This equation was found ro predict vapour pressures with average absolute
and maximum deviiiiiona of O.i3yA a n d 1.43PL respectively.
The vapour pressure data over the tenlperatnre range of 340'~ t o t h e
critical point which covers a r a n g e of pressure of 1.2 atmospheres to
54 atmospheres was fitted t o t h e equation :
4. Suiurated L i p i d und Yapow Dmsr'li~s:
The density of saturated liquid h a s been determired by Morgor: ard
kowrg1$ SchhulzeZ4, Smylh and ~ o r ~ coop3, n ~ 'l'horpe'"
~ , a n 3 by I l r r z sr.6
~ ~ ~ k iThe ~ range available liquid densities o f various invr rt,,ata .,
~ h "o f ~
is prereared in Table-3.

TAXE 3
Sarrrrarm trqwi,f dri~siliesoj'efiiorojbror
--
Year Hnvrriigatar Range of tcmgeratore. "K Kefci-2.c
-
188Q Thorpe 273 - 331 S:
PBL! Schulze "i,6
7
- 299 .;
- +4

1523 Merz a n d Neukirch 506 - 536 10

1928 Morgan a n d Eowry 213 -= 333 IS
1928 Smyth a n d Mo~g:ln 203 - 333 >5
1937 Coop 193 - 293 3

~hor~z~"dctcrmi<isd the dersity o f saturated iiquid up t o tl-e brilirg

point. Thongf. ?he accuracy of !he dara is not mentioned his data agree
w r y closdy wi!'~ those o f Sm:,:h a n d M o r g m a n d Morgan ar.d Lowry, who
claim ;heir volumes t o be dbterrnined iviti: a precision of 1 part i n 1C0.000.
F.am:;zy a n d &'m" have presented some data on the liquid density of
chloroform. T h r i e vaines are stated to be i h o s e of Thorpe.
CoopJ did r o t mention the purity o f t h e sample a n d the accuracy of
ahe data.
Ziqvid deos'i!: at 'iigh lernperatures have bcen d s t e r m i ~ e dby Hcrz a r d
PJc-~kirch-! -Tie sample of c!ilaroform used by these invesiipa~orswas from
Kahlb::cn and w r pi r i f d by drying over cal:iurn chl,,ridc avd curefuiiy
Fraciionatnd The :tccimcy of the density tiara h a s no: bccn mentionsd.
H m a n 3 ~ e - k i r c h have
: ~ also dsterinined saluruied vapour dciisilies of
chioroform over a temperature range o f 4 3 2 t o 536-K.
T h e vapour densitizs over a Temperalure rafige of 2 2 5 ' ~to 430% were
maiuated using Martin a n d 'CPou equation [Equation 5). For this invesliga:ioa
nhs8a:uaatcd liquid densities of Thorpe, Herz and Ncukirch, hlorgan an6 F c n q
a n d Srny!b and M V ~ D Tthe ~ D'iapour
. densities o f Herz and Neukirch and the
d c a l s t e d vapout decsi:ies were combined and a smooth curve m a s d r t w n .
The dmsiiiex of snturaIed liquid wherever not available (over t h e tenlperafure
range of 330'~ t o 5 0 0 ~ ~ )
were evaluated from the smooth curve taking into
cocsider%tionthe observance of tka law of rxti!incar diameters.
 T/zermodynamic Properties of Chiorofortrr 1P3

(4) ~ ~C ~ n p cl i i ynf, the Saturated Liquid :

The hear capacity of saturated liquid has been determined by Wiiliams
,,d ~ a n i s l s " over a large o f temperature of 295 - 3 1 9 ' ~ , by Dolezaiek and
I Z ~a temperature range o f 223 - 2 9 3 ' ~and by Staveley sf
S ~ ~ U over over
a temperature range of 284- 3 3 ' ~ . The extent of purity o f the salnpltr ksed
not reported by these investigators. Kowever StaveIy et 01.'~ &im their
data t o be accurate t o * 174.
For this investigation the heat capacity data of all the investigators were
csmbined, smoothened, and were used. The smoothened data agree with the
actual values wlthin 1%.
(5) H d of fi~poriralion:
Latent heat of vaporization o f ch1oroform has been experimentally
determined by the calorimetric method over a range of temperature of
273 - 314°K by Fletcher and 7yrer7. The values are claimed to be accurate to
~ i t h i n+ 0. ! cal /gm Heats of vaporizalion a t the boiling point have also
been determined by Marsheli", Mathewsis, writzj2 and by Tyrerl' The data
of ~ a t h e w sis' ~ in very good agreement with that of F l e t ~ h e rand ~ ~ r e r ' .
The samples used by ~ a t h e w s were ' ~ checked for purity against density and
refractive index at 2 0 ' ~and by de~errnining the normal boiling point. The
sanples used by ~ y r e r "a n d marshal^'^ were fractionated and the purity of
the sample was checked by the density a n d the boiling point The data of
Fletcher and ~ y r e r 'a t the normal boiling point is about 1% higher than that
of Tyrer and 2% higher rhan those of Marshall end Mathews. The smoothened
data of all the investigators were used for this work.
Heat of vaporization calculated by Ciausius-Clapeyron equation namely,

aprees with the smoothened data with maximum and average absolute
deviations of 1.5% and 0.5:; respectively.
Meat of vaporization above a temperature of 330'~ was evaluated using
the Clnusius-Clapsyron equation.

Meat capacity of ideal gas have been evaluated by Wold3' n p to B

lciupeiature of 5 0 0 and~ ~by Gelles and ~ i t z c r 'up to a temperature of 150ti"K.
The data of vold3' are stated to be accurate to 97%. The data of Gelles and
p i h r s a r e more recent and extend t o a large temperature range. Neocc,
the data of Grlles and Pitzer were used for this work. The data of Gelles
and Pitzer were fitted by the method of least squares to the equation,
q - r r + b ~ + ~ ~ Z + ~ ~ " 641
where a -7.1093
b - 3,6463 :i

c --
2.9613 x
d-8.4214 x 10-"
over a temperature range of 250 - 1 5 0 0 ~ ~ .
Equation [?I fits the data with maximum and average absolute devialions
of 1.17; and 0.43% respectively. For this work Equation [4J with the constanis
zs given abov.; is asrtd.

For !lie calculation of iher:nodyixmic prc,pcr:ies .Martin and Aou

equation of state, namely,

with K - 5.475 h a s been used.

The constants evaluated by the method outlined by the zutbors" are:

Xo tho rango of available data Hqcarion 151 was found to przdici

pressures with average absolute a ~ kmaximum dzviations o f 1.777; and 2.70%
resptcrively.
Speciiic volumes of saturated and superheated vapour were calcula?ed
using Eqnntion [5] by making use of Newton-Raphson iterative method on a:!
9BM it510 digital computer, for various iemperaturcs and pressures.
Entropy and En:nflrolpyoJ zhe Superheated Vapour :
Consldcriag the entropy and cnthalpy t o be funcrions af volunle
7~?0;;erdnre, v. e have,
-
d S (a s/a T),.dT r (3 s/a Y), d v @I
Using Equations 141 and in the aL.ov+ equations and carrying out t h e
integration, we obtain expressions for en:ropy and erilhaipy a s :
Reference State :
The choice of the reference state depends on tbe convenience and !be
information avaihble. The values of the constants of integration
dependent on ihe reference state chosen. Further, the reference state chosen
should facilitate easy cordparison and utilization of the tabulated data.
As has becn pointed out by Canjar and ~ d n n i u the ~ ~ choice
, of the
reference state as H = 0 and S + R In P=O for elenients a t absolute zero
of temperatura and a t zero pressure would be applicable not only for pure
subhtances but also for a rnix:ure of pure sustances that undergo a chemical
reaction. But it is necessary to haOe a knowledge of the heat of formation
o r the compound. In the present work as the heats of formation were
available, the refirence state N - 0 and S + R In P = O for dements at
absolute zero of temperature and r t zero pressure has been used.
Entropy value at ?he normal boiling point was evaluated using the ideal
gas thermodyilzmic properties and the Berthelot correction. Enthalpy at the
normal boiling point was evaluated by making use of the value of -22.8
Kcal./mole for A H ! ,the heat of formation a t oOK, the ideal gas thermo-
dynamic properties and the Berthelot correction for enth: lpy. The integration
constants Cs and CH were evaluated using the values of entropy and enthalpg
at the normal boiling point. The values thus evaluated are:
Cs - 25.30 cal./moie 'I<

Entropy anc! enthalpy of the superheated vapour were evaluated by making

use of the c2l:ulated specific volume in Equation f l . ] and [13].
Bntropy and enthalpy of saturated vapour were evaluated by using the
the experimental specific volumes in Equations [121 and [13]. Wherever the
experimental data we*e not available these wzre calculated using Equation [5]
and were used.

Enrro@y and Enrhalpy of the S ~ l f u r a r ~Liquid

d :
The entropy of vap~rizationis related to the heat of vaporization by rhs
relation
A&- T A S ,
The entropy and enthalpy of the saturated liquid were calculated using the
equations
SI=S* AS, - 1131

The properties of saturated and superheated chloroform are presented

in Tables 5 and 6 and in graphical form as Figure. 1,
 -
j 1 rrMpERntum ENTROPY
FOR Ii
&NO KULOOR N R
P:PRESSURE. ATMOSPHERES --
4
H:ENIHALPY, CALORIES/GRAMMOLI --
!I
BOa.0 V:VOLUME, LITRES/bRAM MOLE ---I--
.-
X: WEIGHT PERCENT -~.&/
I

ENTROPY, CAUIRIESIGRAM MOLE'K

 INTERNAL CONSIS~ESCY
OF THE TAI~UL.ATED
RFS~LTS
The relation d H - T&+ VdPmay be used t o check the intcrnal consis.
tency of the entropy and enthalpy values.
At constant pressure,
dW - TdS [17!

Hence, d H - d (TS)- SdT from which

Internal consistency checks were made for superheated region by using

Equation [IS]. The definite integral in Equation [IS] was evaluated by
Simpson's rule. Tahle 4 gives the comparison o f calculated and tabulated
values of changes of enthalpy A H for 6 isobars.

NOUEKCLATURE
- Constants in Equation [I].
-Constants in Eqaation [2].
-Constants in Equation [4].

- Constants in Equation [5]

- H e a t capacity at constant pressure, cal /%m. mole OK.
- H e a t capacity a t constant voiume, cal./gm mole OK.
-Constants of inregration in Equations [:2] and [UI
respectively.
- Enthaipy, cai / f m . mole.
- PiesBure, atnioi'phercs.
- Gals constant liter at:n/g~n. mole OX.

-Entropy, c a ~ . / ~ mmole
. OK.

- Temperature, O K .
-Specific volume, ~ i t r e s / ~ r nnolc.
.
- H e a t of formatioo a t OOK, cals./grn. mole:
-Enthaipy of vaporization, c a l ~ . , / ~ mmole.
-Entropy of vaporization, cals !gm. m o k O K .

- Broper:ies at zero pressure or ideal gaseous statea

- Critical point.
- Gas or vapout
- Liquid
- Pressure
- Temperature
- Volume,
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 E., and Licsche,
1, ~ ~ c k m a n n O., .. Z. Physik. Cizern., 1914, 88, 23.
canjar, L. N. and Manning, P. S . , .. hTvi.rocorbon Proccsring, 1552,4B.No. 8,121.
!. Ccap. I. E., .. Trans. Fnraday Soc., 1937, 33. 583.
4. Doiezaltk, F. and Schulzc. A . .. Z. Physik. Chcm., 1913. 83,45.
5. nruckci, C . , Jimeno, E.and Kangro. W. %. Physik. Chenr. 1915, 90, 513.
6. Fiacher, R and Rcichel, T.. .. Mikroclwmi~.1943,31, 102.
:. ~!ctchci.J . and Tyrer. D., .. J. Chem. Sac. (London),l913,E03. 104, 517.
'. ~ d l c s E.
. 3 r d Pirzer, X . S . . .. Z . 1953,75,5259.
J. Am. C ~ E I ISnc.,
4. Hzrand, 1.. .. hfo,iafsch. 1935, 65,153.
:o. Herz, W. and NeukircR, E.. .. Z.Physik. Chem., 1923, 8 0 4 . 435,
11. Z C ~ Z
W., and Rathmann, W.. .. Chem. Zrg., 1913, 36. 1417.
12 Kuenen, J . P. and Robson, W. G . , .. Phil. Mag., 1902, 4. 121.
!3. Marshall, D., .. Phi!. Mac. 1897,43, 27.
13. Martin. J.J. and Nou, Y. C.. .. A . I. Ch. E. Iownol, 1954, 1. 142.
15. Mathews. J . H., .. J. Am. Chem. Sac.. 1926. 48, 562.
16. Morgan, S. 0.and Lowry, N.M., .. J . Phys. C1,nn. 1930. 34. 2385.
17. Pictet, R. and Altschul, M . , .. Z. Physik. Chent.. 1895, 16. 26.
;S. Bsmsay, W . and Anton, E., .. Proc. Roy. Soc. London, i894,56, I S P .
19. Rex, R.. .. Z Pi~ysil:.Ctiern., 1916. $5. 355.
ill. Sajotrchewsky, W.. .. Beibl. Ann. Pizysik., 1879. 3, 741.
21. Scatchard, G . aad Raymonds, C L.. .. 3. Am. Chem. Suc. 1938. 60. 1278-87.
22. Schmidt. C . C . , .. Z . Phyrik. Cirem. 2921, 99,71.
23. -, .. Ibid, 1926, 121, 221.
24. S c h u l ~ e A.,
, .. Ibid, 1921, 97,388, 417.
25. Smytb, C.P. and Morgan, S.O., .. I.Am. Chem. SOc., 1928, 50, 1547.
26. Slaveley, L. A.K., Tugman, W.F. and .. Trans. Faradoy. Sac., 1955,51, 323
Hart, K.R.,
27. Stul!, D. R . .. Ind Eng. Ciwm., 1947,39, 5x7.
28. Thorpe, T. E., .. Tmns. Clrenr. Soc., 1880, 37, 59.
29. Tyrer, D., .. J . Chenr. Soc. London, 1911,99, t633.
30. Void, R . D . .. J. Am. Chem, Soc.. 1935.57, 1192.
31. Williams, J. IV. and Daniels, F., .. lbid, 1925. 47, 1490.
32. Wirtz, K., .. Ann. Physik.. 1890. 40,439.
".,
2,. ,. Internarional Critical Tablcs, Vols. 3 ~ n l d
5. McGraw-tiill, York, 1929.