Vapor Pressure and Heat of Vaporization

Valentin Uzunov (author) & Francesca Frattaroli (lab partner)

PSU ID#: 96!""#$$
%&' (()&* +ab (6!* Due (!,"(,!
ABSTRACT
-he current e.peri/ent ai/e0 to 0eter/ine the i0entit1 o2 an un3no4n pri/ar1 alcohols 2ro/ its
heats o2 vaporization5 -he heat o2 vaporization 2or an un3no4n sa/ple 4as 0eter/ine0 2ro/
e.peri/ental 0ata collecte0 on the chan6e in vapor pressure 4ith increasin6 te/perature5 Data 4as
processe0 usin6 the %lausius7%lape1ron e8uation to 0eter/ine the enthalp1 o2 vaporization 2ro/ the
slope o2 the line o2 best 2it5 -4o un3no4ns 4ere tests5 -he 0eter/ine0 enthalp1 o2 vaporization 2or
Un3no4n #! an0 #( 4ere: #)596 3: , /ol (7#59;)* an0 9#59) 3: , /ol ( ((5$;) respectivel15 Fro/
the results it 4as conclu0e0 that un3no4n #! 4as ethanol* an0 it 4as speculate0 that un3no4n #(
4as Isoprop1l5 <66re6ate0 results support the results 2or un3no4n #( reportin6 an enthalp1 o2
vaporization o2 #59( 3: , /ol = #5" (( s0)* 7"5!); error 0i22erence 2ro/ literature value o2
Isoprop1l5
INTRODUCTION
-he purpose the current investi6ation 4as to 0eter/ine the enthalp1 o2 vaporization (>&vap) 2or an
un3no4n pri/ar1 alcohol at stan0ar0 te/perature an0 pressure (S-P)* as /eans o2 i0enti2ication5
Usin6 e.peri/entall1 6athere0 0ata on the chan6es in vapor pressure 4ith respect to increasin6
te/perature* the >&vap can be anal1ticall1 ascertaine0 2ro/ the 0ata5 It 4as e.pecte0 that the the
enthalp1 o2 vaporization 0eter/ine0 2ro/ the 0ata collecte0 4ill be close to accepte0 literature
values5
?vaporation o2 substance open to the at/osphere is 0epen0ent on the sur2ace area e.pose0 to the
at/osphere* its te/perature* an0 the stren6th o2 the cohesive inter/olecular 2orces (I'F)5 <t an1
one ti/e* so/e /olecules in the sa/ple 4ill have /ore ther/al ener61 then the sa/ple avera6e an0
4ill thus be able to brea3 2ree at the li8ui0 sur2ace* an0 escape as 6as5 -he transition 2ro/ li8ui0 to
6as is 3no4 as vaporization an0 the reverse process is 3no4 as con0ensation5 Un0er nor/al
con0itions evaporation an0 con0ensation are si/ultaneousl1 occurrin6* ho4ever evaporation ta3e
place at a 6reater rate as the particles that evaporate* escape in to the at/osphere an0 are not
reabsorbe05 @e observe this pheno/enon as a 0ecrease in volu/e o2 the li8ui0 over ti/e5 +i8ui0s
4ith 4ea3 I'F ten0 to have hi6her evaporation rates because less ther/al ener61 is re8uire0 to
overco/e the I'F hol0in6 sur2ace /olecules 2ro/ vaporizin65 Substances that evaporate easil1 at
roo/ te/perature are re2eree0 to as bein6 volatile5
@hen a volatile li8ui0 is seale0 in a container* the partial pressure o2 the li8ui0 vapor be6ins to
increase as vapor 6as buil0s up in the container5 <s the pressure insi0e the container increases the
con0ensation rate be6ins to be 2avore0 over evaporation* 0ue to the no4 6reater overall li8ui0 6as
interaction5 ?ventuall1 a point o2 e8uilibriu/ is reache0 4here the rates o2 evaporation an0
con0ensation are e8ual5 <t this point the partial pressure o2 the 6as beco/es constant an0 the 6as
an0 li8ui0 phases are sai0 to be in 01na/ic e8uilibriu/5 -he pressure o2 a 6as in 01na/ic
e8uilibriu/ 4ith its li8ui0 is calle0 vapor pressure5
&eat o2 vaporization a3a enthalp1 o2 vaporization* is the ener61 re8uire0 2or ! /ole o2 a substance
to transition 2ro/ a li8ui0 to a 6as at a 6iven pressure5 -he enthalp1 o2 vaporization can be
e.presse0 as
H
vap
= U
vap
p V
A?8 !B
4here CUvap is the internal ener61 o2 the vapor phase co/pare0 4ith the li8ui0* an0 pCV is the
4or3 0one e.pan0in6 the s1ste/ a6ainst its surroun0in6s5 -he increase in internal ener61 o2 the
vapor is the ener61 re8uire0 to overco/e the cohesive inter/olecular 2orces hol0in6 the li8ui0
to6ether5 ?nthalp1 o2 vaporization is partiall1 te/perature70epen0ent* 0i/inishin6 4ith increasin6
te/perature an0 vanishin6 co/pletel1 at the critical te/perature o2 the substance* 4hen the li8ui0
an0 vapor transition into a super supercritical 2lui05
Darai ((""9) has propose0 an e.planation 2or the li8ui076as phase transition process 2or a
/onoato/ic li8ui0s5 &is /o0el su66ests that the ener61 re8uire0 to 2ree an0 ato/ 2ro/ the li8ui0 is
e8uivalent to the ener61 nee0e0 to overco/e the sur2ace resistance o2 the li8ui05 -he /o0el 4as
success2ull1 use0 to calculate0 latent heat o2 vaporization values 2or 9 ele/ents an0 see/s li3e it
coul0 also 0escribe0 the ph1sical processes 2or s/all /olecular li8ui0s5 'ore co/ple. /o0els to
e.plain the ph1sical process 2or lar6er /olecules are still 0ebate05 Diven the size o2 the li3el1
/olecules investi6ate0 its presu/e0 that DaraiEs /o0el coul0 be applicable to conceptuall1 0escribe
process o2 the current investi6ation5
-he relationship bet4een vapor pressure an0 te/perature is e.ponential* s/all chan6es in
te/perature can have lar6e e22ects on the vapor pressure5 -his relationship can be e.presse0 as
2ollo4s:
P
vap
=
Hvap
RT
A?8 (B
4here F is constant that 0epen0s on the 6as* C&vap is the chan6e in enthalp1 o2 vaporization (heat
o2 vaporization)* G is the i0eal 6as constant ()5#! : , /ol H I)* an0 - is te/perature in 3elvins5 -his
e8uation can be rearran6e0 into a 0i22erent 2or/* 3no4 as the %lausius7%lape1ron e8uation
ln( P
vap
) =
H
vap
R
(
!
T
)
+ ln( )
A?8 #B
-here is parallel relationship bet4een the %lausius7%lape1ron e8uation an0 the e8uation 2or a
strai6ht line5 < plot o2 the natural lo6 o2 vapor pressure an0 the inverse te/perature pro0uces a
linear relationship 4ith a slope e8ual to the enthalp1 o2 vaporization over the i0eal 6as constant*
4hich can then be solve0 to 1iel0 the C&vap5 Its i/portant to ac3no4le06e that in usin6 the
e8uation in this 4a1* the te/perature 0epen0ence o2 C&vap is i6nore0* 4hich is relativel1 s/all but
i/portant to ac3no4le06e5
<n i/portant a00itional step in 0eter/inin6 the correct chan6e in vapor pressure 4ith increasin6
te/perature in the current e.peri/ental proce0ure* 4as to correct 2or the partial pressure o2 air
seale0 in the container 0urin6 the e.peri/ent5 -he partial pressure contribution o2 air to the total
pressure /easure/ent can be 0eter/ine0 2ro/ the Du17+ussac +a4 2ro/ an initial base rea0in65
P
initial
T
initial
=
P
final
T
final
A?8 B
J1 ta3in6 the 0i22erence bet4een the total pressure /easure0 an0 the partial pressure o2 air* the
vapor pressure o2 the li8ui0 can be 0eter/ine0 an0 use0 in subse8uent calculation an0 0ata anal1sis
to i0enti21 the sa/ple co/poun05
EXPERIMENTA
In this e.peri/ent* an un3no4n pri/ar1 alcohol 4as seale0 in a 2las3 an0 6ra0uall1 heate0 in a
4ater bath5 -he pressure an0 te/perature o2 the air an0 alcohol vapor /i.ture insi0e the 2las3 4as
/easure0 usin6 a pressure sensor attache0 to the 2las3 an0 a te/perature probe in the 4ater5 -he air
partial pressure contribution is accounte0 2or* b1 ta3in6 an initial pressure rea0in6 o2 the seale0
vessel be2ore the un3no4n is a00e0 to the 2las35 -he te/perature an0 pressure are /easure0 over a
course o2 976 trials 4ith the te/perature bet4een trials increasin6 b1 #79 K%5
DATA
Ta!"e # L 'easure vapor pressure chan6es 4ith increasin6 te/perature 2or Un3no4n #!
Initial -rial ! -rial ( -rial # -rial -rial 9
-e/perature
( K% )
19.65 !9569 ((5)9 (9599 #"5(9 #59
-otal Pressure
( -orr )
)65$!6 )$(5(9( )995") 9!56 9))5$6
<ir Pressure
( -orr )
$9"5)) $9"5)) $995")6# $6$5"#6( $$)5"6#9 $))5)##
Vapor Pressure
( -orr )
95.836 !!#5!69$ !#(5"#) !6#59$69 !9959(9$
Ta!"e $ L 'easure vapor pressure chan6es 4ith increasin6 te/perature 2or Un3no4n #(
Initial -rial ! -rial ( -rial # -rial -rial 9
-e/perature
( K% )
19.85 !9569 (#5!9 ($5#9 #"5"9 ##5#9
-otal Pressure
( -orr )
$)95#) )"(5"() )#5#() )9#5) )$5#)
<ir Pressure
( -orr )
$9!5##6 $9"5)(#! $995$9)! $$"596)( $$$59!$ $)9599#9
Vapor Pressure
( -orr )
34.56086 (5((9)9 6#5$99)9 $959))() ))5(6!#
Ta!"e % L ?nthalp1 o2 Vaporization a66re6ate results per Un3no4ns
>&vap (3:,/ol)
Un3no4n #!
>&vap (3:,/ol)
Un3no4n #(
>&vap (3:,/ol)
Un3no4n ##
#!5#
9#59)
69.63 (95##
62.94 9569
13.93 50.33
#$5(" 31.29 34.02
'ean = (s0 43.92 = 43.40 41.08 = 27.51
RESUTS & DISCUSSION
Ta!"e ' L Pressure chan6e 4ith increasin6 te/perature 2or Un3no4n #!
-e/p ( I )
-otal
Pressure
( at/ )
<ir Pressure
( at/ )
Vapor
Pressure
( at/ )
ln( Pvapor ) !,-
Initial (9(5) "59))"
-rail ! (9(5) !5!!! "59))" "5!(6! 7(5"$"$ "5""#!9#
-rial ( 296.0 1.1477 "599)) "5!)9 7!59"9 "5""##$)
-rial # 299.1 1.1830 !5""9# "5!$#$ 7!5$9"( "5""###
-rial 303.4 1.2390 !5"(#) "5(!9( 7!59#6" "5""#(96"
-rial 9 306.6 1.3010 !5"#6 "5(66 7!5#((6 "5""#(6!6
-he results reporte0 in -able * sho4 the e.peri/ental results o2 vapor pressure as te/perature
increases 2or Un3no4n #!5 -he overall chan6e in vapor pressure 4as !"$ -orr ("5!"# at/) over a
!#5) K% interval5 -hese results 2it the e.pecte0 rise in vapor pressure 4ith te/perature 2or a volatile
li8ui05 Fi6ure ! illustrates that e.pecte0 e.ponential relationship bet4een the controle0 variables5
-he e.ponential rise in vapor pressure is a result o2 the avera6e ener61 0istribution in the s1ste/
4hich 2ollo4s a 'a.4ell7Joltz/an 0istribution5 <s heat is absorbe0 an increasin6l1 6reater
proportion o2 sur2ace /olecules have su22icient ener61 to vaporize5
Figure 1 shows an clear exponential relationship between vapor pressure and temperature for
unnown li!uid "#$ f%x& '()$*+x exp%,$,-+))x&. R
*
' ,$+++/
18 20 22 24 26 28 30 32 34 36
0
50
100
150
200
250
Temperature (C)
V
a
p
o
r

P
r
e
s
s
u
r
e

(

T
o
r
r

)
@hen the 0ata is processe0 usin6 the %lausius7%lape1ron e8uation the pre0icte0 linear relationship
bet4een the natural lo6 o2 vapor pressure an0 te/perature in 3elvin is pro0uce0* as sho4n in 2i6ure
(5 Fro/ the slope o2 the line in 2i6ure (* enthalp1 o2 the vaporization 4as 0eter/ine0 to be #$5("
3: , /ol5 %urrent results are closel1 co/parable to the accepte0 literature value o2 enthalp1 o2
vaporization 2or ethanol (at S-P)5 -he >&vap 2or ethanol is 8uote0 in literature as #)596 3: , /ol
A(B* 4hich is 7#59; 0i22erence error to current results5 -he s/all 0i22erence in values coul0 be
potentiall1 attribute0 to e8uip/ent precision* i6norin6 the s/all te/perature 0epen0ence o2 >&vap
an0 or the relativel1 2e4 repetitions o2 e.peri/ent5 It is e.pecte0 that 4ith /ore repetitions 6iven
si/ilar stan0ar0 o2 precision* a ver1 close /atch bet4een values coul0 be achieve05 -here 4ere no
a66re6ate results to co/pare the current results a6ainst* thus variabilit1 o2 results is un0eter/ine05
Ta!"e ( L 'easure pressure chan6e 4ith te/perature 2or Un3no4n #(
-rial -e/p (I)
-otal
Pressure
(at/)
<ir Pressure
(at/)
Vapor
Pressure
(at/)
ln( Pvapor ) !,-
Initial 293.0 "59))6
-rail ! (9(5) !5"## "59)$9 "5"99 7#5"9"6 "5""#!9
-rial ( 296.3 1.0553 "5999$ "5"996 7(5)9"( "5""##$9
-rial # 300.5 1.0978 !5"!#9 "5")#9 7(5$)( "5""##()
-rial 303.2 1.1230 !5"(#" "5!""" 7(5#"($ "5""#(9)
-rial 9 306.5 1.1505 !5"#! "5!!6 7(5!9!( "5""#(6#
-he results 2or a secon0 un3no4n* Un3no4n #(* 4ere also 0eter/ine0 an0 0ispla1e0 in -able 95
-he overall chan6e in vapor pressure 4as 9#59 -orr ( "5"$"9 at/) over a !#5$ K% interval5 -he
results sho4 that Un3no4n #( has a 6reater >&vap co/pare0 to Un3no4n #! over the te/perature
Figure 2 0hows a stron1 linear relationship between the natural lo1 of vapor pressure and
inverse of temperature for unnown li!uid "# as per 2lausius32lape4ron e!uation$ Function of
line of re1ression is f%x&' 3--5-$6*x 7 #($*#. with an R
*
value of #$,,,
3.20E-03 3.25E-03 3.30E-03 3.35E-03 3.40E-03 3.45E-03
-3
-2.5
-2
-1.5
-1
-0.5
1/T ( 1/K )
L
n

P

(
P

i
n

a
t
m
)
ran6e selecte05 -his su66ests that that the I'F 4ithin Un3no4n #( are stron6er* li3el1 0ue to a
6reater contribution o2 0ispersion 2orces bet4een /olecules* as 4ell as su66est that Un3no4n #(
has a hi6her /olar /ass5 Fi6ure # sho4s less obvious e.ponential relationship bet4een vapor
pressure an0 te/perature co/pare0 to results 2or Un3no4n #!5

Figure 4 0hows a stron1 linear relationship between the natural lo1 of vapor pressure and
inverse of temperature for Unnown "* as per 2lausius32lape4ron e!uation$ Function of line of
re1ression is f%x&' 3)-+($*#x 7 #+$,/. with an R
*
value of ,$+/),
Fi1ure ( 0hows a ver4 1radual exponential relationship between vapor pressure and
temperature for Unnown "* over the temperature ran1e measured$ f%x& ' ))/$-x
exp%,$,,/,55x&. R
*
',$++65
18 20 22 24 26 28 30 32 34 36
740
760
780
800
820
840
860
880
900
Temperature ( C )
V
a
p
o
r

P
r
e
s
s
u
r
e

(

T
o
r
r

)
3.25E-03 3.30E-03 3.35E-03 3.40E-03 3.45E-03
-4
-3.5
-3
-2.5
-2
-1.5
-1
1/T (1/K)
l

P

(
P

!

a
t
m
)
Processin6 the 0ata 4ith the %lausius7%lape1ron e8uation pro0uce0 the e.pecte0 linear relationship
as sho4n in Fi6ure 5 -he lo4er coe22icient o2 re6ression su66ests that e.peri/ental results are less
precise then those 6athere0 2or Un3no4n #!* an0 thus a potential si6ni2icant source o2 error to
consi0er5 Fro/ the slope o2 the linear e8uation 2ittin6 the 0ata* the enthalp1 o2 the vaporization 4as
0eter/ine0 to be 9#59) 3: , /ol5 -hese results 0o not /atch an1 o2 the pri/ar1 alcohols un0er
consi0eration5 -he closest /atch in >&vap values 4as Isoprop1l alcohol* 4hich has a value o2 5"
3: , /ol A#B* ho4ever there is still a ((5$; error 0i22erence bet4een current results an0 the literature
value5
-he lar6e 0i22erence in results 2ro/ literature* is believe0 to be lar6el1 0ue to e.peri/ental error*
an0 precision5 Its speculate0 that the te/perature ran6e use0 in the e.peri/ental proce0ure 4as to
lo4 to accuratel1 capture the chan6e in pressure 4hich coul0 be /a6ni2ie0 b1 calibration error or
sensitivit1 o2 the instru/ents use05 @ith /ore trials* over a 6reater te/perature ran6e* an0 repeate0
proce0ures a better results 4oul0 be e.pecte05
-he reporte0 a66re6ate0 results 2or Un3no4n #( sho4 a /ean >&vap o2 #59( = #5" (( s0)* a
7"5!); error 0i22erence to the literature value5 &o4ever the vali0it1 o2 the result is 8uestionable 0ue
the lar6e stan0ar0 0eviation5 -he lar6e variabilit1 bet4een results reporte0 i/plies inconsistent
e.peri/ental proce0ure stan0ar0s bet4een 6roups5
CITATION
A!B Darai* :5 ((""9)5 MPh1sical /o0el 2or vaporizationM5 Fluid Phase 8!uilibria5 ()#: )9L$$5
http:,,0.50oi5or6,!"5!"!6,N52lui05(""95"65""9
A(B ?thanol (0ata pa6e)5 (("!#* Dece/ber 6)5 In 9iipedia. The Free 8nc4clopedia5 Getrieve0
!9:"9* Februar1 ("* ("!* 2ro/ http:,,en54i3ipe0ia5or6,4,in0e.5phpO
titleP?thanolQ(0ataQpa6e)&ol0i0P9))(9$!
A#B Isoprop1l alcohol (0ata pa6e)5 (("!* Februar1 (")5 In 9iipedia. The Free 8nc4clopedia5
Getrieve0 (":9$* Februar1 ("* ("!* 2ro/ http:,,en54i3ipe0ia5or6,4,in0e.5phpO
titlePIsoprop1lQalcoholQ(0ataQpa6e)&ol0i0P996(9"6"
CACUATIONS