M. Hristova, D. Damgaliev, D.

Popova
19
Journal of the University of Chemical Technology and Metallurgy, 45, 1, 2010, 19-24
ESTIMATION OF WATER-ALCOHOL MIXTURE FLASH POINT
M. Hristova, D. Damgaliev, D. Popova
University of Chemical Technology and Metallurgy
8 Kl. Ohridski, 1756 Sofia, Bulgaria
E-mail: mariana_hristova@abv.bg
ABSTRACT
Mxu:cs aI vnc: v naas n:c npa:nn n nunc:aus cngncc:ng nppnans. Knavcugc aI nxu:c Ins
pans s nccucu Ia: c: snIc nnung, sa:ngc nnu :nnspa:nan. A p:acuu:c Ia: c csnnan aI Ins pans aI
vnc:-naa nxu:cs l, usng c cqunans aI Mn:gucs, vnn Inn: nnu Wsan s p:cscncu n s pnpc:.
Kc,va:us: Ins pan, nxu:c, vnc:-naa.
Received 05 November 2009
Accepted 12 January 2010
INTRODUCTION
Ilammable substances are commonly useo in
laboratories ano inoustrial processes. Tle llasl point is
one ol tle most important plysical properties useo to
oetermine tle potential lor lire ano explosion lazaros
ol liquios [1]. Tle llasl point is also useo lor tle classi-
lication ano labelling ol oangerous substances ano prepa-
ration in accoroance witl Directive 67f548 IIC ano
1999f45fIC respectively [2,3]. !t sloulo be noteo tlat
tlese Directives will be repealeo ano replaceo witl tle
I\ Regulation on classilication, labelling ano packag-
ing ol substances ano mixtures, implementing tle Glo-
bally Harmoniseo System (GHS) in tle I\ [4].
Tle llasl point ol a given liquio is tle experi-
mentally oetermineo temperature aojusteo to stanoaro
sea level atmospleric pressure ol 76 mmHg (.1 MPa)
at wlicl a substance emits sullicient vapour to lorm a
combustible mixture witl air [5]. A lower llasl point
value inoicates tlat a liquio is more lazaroous relative
to an analogue witl a ligler value [6].
Key to tle oelinition ol tle llasl point ol a liq-
uio is tle specilic test wlicl las been useo. Iacl inoi-
vioual test type may proouce sligltly oillering llasl
points lor tle same liquio. Wlen reporting tle llasl
point, it is important to specily exactly wlicl test las
been useo.
Tlere are two metloos lor tle measurement ol
tle llasl point value ol a liquio - tle closeo-cup test
ano tle open-cup test [6]. Tle open-cup llasl point value
is, typically, a lew oegrees greater tlan tle closeo-cup
llasl point value.
Tle llasl point oata lor pure substances can be
obtaineo lrom various sources, sucl as MSDS (Material
Salety Data Sleets). MSDS are available online lrom a
variety ol sources, incluoing venoor websites lor tle
major sellers ol clemicals.
Still llasl point oata lor a variety ol liquio mix-
tures are scarce in tle literature. Tle total claracteriza-
tion ol a mixture requires signilicant experimental work
ano time. !l a llasl point preoiction mooel lor a binary
mixture coulo be successlully oevelopeo, tle llasl points
Journal of the University of Chemical Technology and Metallurgy, 45, 1, 2010
20
ol various liquio solutions woulo be preoicteo relatively
easily lrom a limiteo number ol initial oata.
Several metloos lave been oevelopeo lor tle
preoiction or estimation ol tle llasl points ol pure com-
pounos ano mixtures. We recently publisleo a review
ol most ol tlese metloos [7].
Tle purpose ol tlis work is to oevelop a proce-
oure lor tle estimation ol llasl points ol binary aque-
ous-organic solutions by using tle equations ol
Margules, van Laar ano Wilson as well as to estimate
tleir aovantages.
Mixtures ol water witl alcolols are important in
numerous engineering applications. Aqueous solutions
ol various alcolols were selecteo lor investigation in
tlis stuoy.
THEORETICAL
Tle properties ol mixtures are oillicult to pre-
oict, because a simple mixing rule will not work wlen
interactions among tle mixture components are strong
[8]. Tle llasl point ol a liquio mixture oepenos on tle
composition ol tle mixture ano on tle types ol clemi-
cal involveo.
Matlematically, tle llasl point is tle tempera-
ture at wlicl tle vapour pressure is equivalent to tle
lower llammable limit in air:
,
( )
sat
i fp f
i
P T
LFL
P
(1)
wlere:
,
( )
sat
i fp f
P T - vapour pressure at tle llasl point tempera-
ture, xHa;
H - ambient pressure, xHa.
Tle vapour pressure ol a mixture ano conse-
quently - its llasl point is allecteo by tle preoominant
interactions (intermolecular lorces) among tle mol-
ecules.
Tle llasl point ol a binary mixture can be esti-
mateo by tle mooel oevelopeo by Liaw et al. [9]:

2
1
,
1
sat
i i i
sat
i
i fp
x P
P

(2)
wlere x

, }

,
sat
i
P , ano
,
sat
i fp
P are tle mole lraction, activ-
ity coellicient, vapour pressure at temperature T, ano
vapour pressure at tle llasl point ol tle mixture com-
ponents, respectively. Tlis mooel is tle result ol com-
bination ol equation (1) witl a Le Clatelier's rule lor
tle llammable vapour-air mixture ol two components
witl tle assumption tlat tle liquio ano vapour plase ol
tle mixture are in equilibrium, ano tle vapour plase is
belaving as an ioeal gas.
Tlermooynamically, tle relation between an ioeal
vapour ano a non-ioeal liquio is representeo in equa-
tion (3):
sat
i i i i
y P x P or
sat
i i i
i
x P
y
P

(3)
Tle llasl point ol a binary mixture can be esti-
mateo by equation (4):

1
, 2
2 2 2
, 1
1 1 1
+
sat
fp
sat
sat
fp
sat
P
P x
P
P x
(4)
Tle temperature tlat satislies equation (4) is tle
llasl point temperature ol tle mixture.
A binary aqueous mixture contains water ano a
llammable component. Water is a non-llammable com-
ponent, ano tlerelore las no T
I
. Tle lowest llasl point
tlat tlese mixtures can exlibit is tle llasl point ol tle
llammable component. Tle preoiction mooel lor aque-
ous solutions is a reouceo version ol tle original Liaw
mooel [1]:
1 1 1
1,
sat
sat
fp
x P
P

2 2 2
2,
1
sat
sat
fp
x P
P

+
(5)
Water is assumeo to be component 1 ano tle
llammable compouno is component 2. Irom equation
(5)
2
sat
P is:
2,
2
2 2
sat
fp sat
P
P
x

(6)
Antoine's equation may be useo to estimate
vapour pressure:
M. Hristova, D. Damgaliev, D. Popova
21
log
sat i
i i
i
B
P A
t C

+
(7)
Tle activity coellicient
2
can be estimateo by
tle use ol several equations, sucl as tle Margules equa-
tion [11], tle van Laar equation, tle Wilson equation
[12], tle RTL equation [13], or tle \!Q\AC equa-
tion [14].
Ior an ioeal solution, tle activity coellicient ol
tle liquio plase lor any component is equal to unity,
ano equation (6) can be reouceo to:
2,
2
2
sat
fp sat
P
P
x

(8)
FLASH POINT ESTIMATION PROCEDURE
Tle Liaw mooel was useo to preoict tle llasl
point ol tle lollowing binary aqueous solutions: water-
metlanol, water-etlanol, water-n-propanol ano water-
isopropanol. Tle preoiction results were compareo witl
experimentally-oeriveo oata [1].
Tle inlormation neeoeo lor tle estimation ol a
binary mixture llasl point is:
llasl points ol tle inoivioual components ol
tle mixture;
vapour pressure ol eacl mixture component;
activity coellicient ol eacl component.
Tle saturateo vapour pressure ol tle pure sub-
stance, , at its llasl point,
,
sat
i fp
P , as presenteo in Ig. (5),
can be estimateo by substituting tle llasl point ol com-
ponent into Antoine's equation.
Tle aqueous solutions are non-ioeal solutions,
ano tle activity coellicients are oillerent tlan unity.
Iacl activity coellicient can be calculateo by tle
Margules equation, van Laar equation or Wilson equa-
tion:
Table 1. Parameters lor tle Margules, van Laar ano Wilson equations [16].
Margules van Laar Wilson
System

A

B

A B

cal/mol cal/mol
Water (1) -
Methanol (2)
0,5434 0,7923 0,5619 0,8041 520,6458 82,9876

Water (1) -
Ethanol (2)
0,7947 1,6022 0,9227 1,6798 953,2792 325,0757
Water (1) -
n-Propanol (2)
0,7172 2,7070 1,1572 2,9095 1396,638 906,5256
Water (1) -
Isopropanol (2)
0,8976 2,3319 1,0938 2,4702 1230,208 659,5473

Table 2. Antoine coellicients lor tle involveo components
*
.
Component A B C
Methanol 8,0724 1574,99 238,7
Ethanol 8,2133 1652,05 231,48
n-Propanol 7,6192 1375,14 193,01
Izopropanol 8,1182 1580,92 219,62

0
lg ( )
B
P mmHg A
t C C

, ] +
]
*
Journal of the University of Chemical Technology and Metallurgy, 45, 1, 2010
22
Fig. 1. Comparison of the estimated water (1)- methanol (2)
mixture flash points with experimental data.
Fig. 2. Comparison of the estimated water (1)- ethanol (2)
mixture flash points with experimental data.

Component

CAS
number
T
Ip
(
o
C)
T
boil

(
o
C)
M
(kg/kmol)
p
(g/cm
3
)

(cm
3
/mol)

Methanol 67-56-1 10,0 64,7 32,04 0,7867 40,73
Ethanol 64-17-5 13,0 78,4 46,07 0,789 58,68
n-Propanol 71-23-8 23,0 97,2 60,1 0,8003 75,09
Isopropanol 67-63-0 13,0 82,3 60,1 0,7853 76,53
M/p

Table 3. Claracteristics ol tle stuoieo alcolols.
Fig. 3. Comparison of the estimated water (1)- propanol (2)
mixture flash points with experimental data.
Fig. 4. Comparison of the estimated water (1) - isopropanol
(2) mixture flash points with experimental data.
*
i
V
M. Hristova, D. Damgaliev, D. Popova
23
Margules
2
2 2 1
ln ( 2( ) ) B A B x x + (9)
van Laar
2
1
2
1 2
ln
Ax
B
Ax Bx

, ]

, ]
+
]
(1)
Wilson
12 21
2 1 21 2 1
1 2 12 1 21 2
ln ln( ) x x x
x x x x

j \
+
, (
+ +
( ,
(11)
2 12
12
1
exp
V A
V RT
j \

, (
( ,
;
1 21
21
2
exp
V A
V RT
j \

, (
( ,
(12)
wlere
i
V - molar volume in cm
3
fmol
R - universal gas constant calfmol
T - temperature in K.
RESULTS AND DISCUSSION
Ilasl point preoictions assuming non-ioeal
belaviour using tle oillerent G
ex
(an excess lree Gibbs
energy) mooels were perlormeo by iterative calculations
in MatlLab.
Tle relevant parameters lor tle equations to cal-
culate tle activity coellicients lrom literature are listeo
in Table 1. Tle Antoine coellicients lor tlese substances
were aoopteo lrom literature sources [15] ano are listeo
in Table 2. Table 3 presents tle parameters lor tle pure
components, neeoeo lor tle application ol tle Wilson
equation.
Tle preoictions lor tle water-alcolol mixtures
are presenteo in Iigs. 1-4. Calculateo llasl points by
using tle oillerent equations lor activity coellicients are
comparable witl tle experimental oata obtaineo lrom
Liaw et al [1]. Larger oeviations between tle ioeal pre-
oicteo values ano experimental oata are obtaineo witl
increasing water content (x
1
~ .8) lor tle mixtures
water-metlanol ano water-etlanol. Tle llasl point ol
tle water-etlanol mixture, preoicteo by tle ioeal solu-
tion mooel is ligler - approximately 2
o
C, wlen x
1

.9. Ior tle water-propanol ano water-isopropanol mix-
tures, tle ioeal solution mooel preoicts ligler llasl
points values lor x
1
~ ,4 - ,5. Wilson's equation is
more ellective lor oilute compositions tlan Margules
or van Laar equations.
CONCLUSIONS
Tle calculateo llasl points ol water-alcolol mix-
tures are in a gooo agreement witl experimental oata.
Iquations lor activity coellicients estimations are wioely
useo because ol tleir llexibility, simplicity, ano ability
to lit many systems. Wilson's equation is more ellective
lor oilute compositions tlan tle equations ol Margules
or van Laar.
REFERENCES
1. D.A.Crowl, 1.I Louvar, Clemical process salety: lun-
oamentals witl applications, Inglewooo Clills, .Y.,
Printice-Hall, 199.
2. Council Directive 67f548fIIC ol 27 1une 1967 on
tle approximation ol laws, regulations ano aominis-
trative provisions relating to tle classilication, pack-
aging ano labelling ol oangerous substances.
3. Council Directive 1999f45fIC ol31 May 1999 con-
cerning tle approximation ol laws, regulations ano
aoministrative provisions relating to tle classilica-
tion, packaging ano labelling ol oangerous prepara-
tions.
4. Regulation (IC) 1272f28 ol tle Iuropean Parlia-
ment ano ol tle Council ol 16 December 28 on
classilication, labelling ano packaging ol substances
ano mixtures - amenoing ano repealing Directive
67f548fIIC ano 1999f45fIC, ano Regulation (IC)
o 197f26.
5. CCPSfA!ClI, Guioelines lor Ingineering Desing lor
Process Salety, American !nstitute ol Clemical In-
gineers, ew York, 1993.
6. I.P.Lees, Loss Prevention in tle Process !noustries,
vol.1, 2no eo., Butterwortl-Heinemann, Oxloro, \K,
1996.
7. M.Hristova, S. Tclaouslev, 1. \niv. Clem. Teclnol.
Met. (Solia), ", 3, 26, 291-296.
8. M Vioal, W.1.Rogers, M.S.Mannan, Process Salety
Journal of the University of Chemical Technology and Metallurgy, 45, 1, 2010
24
ano Invironmental Protection, &", (B1), 26, 1-9.
9. H.1. Liaw, Y.H.Lee, C.L. Tang, 1. ol Loss Prev. in tle
Proc. !no., #, 6, 22, 429-438.
1. H.1. Liaw, Y.Y Cliu, 1. Haz. Mater., ), 23, 83-16.
11. H.C.Carlson, A.P.Colburn, !no.Ing.Clem., !", 1942, 581.
12. G.M. Wilson, 1.Am.Clem.Soc., &$, 1964, 127-13.
13. H. Renon, 1.M. Prausnitz, A!ClI 1ournal, 14, 1968,
135-144.
14. D.S. Abrams, 1.M.Prausnitz., A!Cle 1ournal, 21,
1975, 116-128.
15. R.C.Reio, 1.M.Prauznitz, T.K. Slerwooo, Tle Prop-
erties ol Gases ano Liquios, 3ro eo., McGraw-Hill,
ew York, 1977.
16. 1. Gmelling, \. Ouken, Vapor-Liquio Iquilibrium
Data Collection, DICHIMA Clemistry Data, v.1
(parts 1-1), Iranklurt, 1977.