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Abstract— The determination of the experimental latent heat of interface to liquid phase because of pressure build up. As the
vaporization of ethanol was accomplished using the Ramsay- rate of transfer from one phase to another becomes equal, the
Young Method. Saturation temperature values were obtained system goes into dynamic equilibrium and consequently,
by varying vacuum pressures. Experimental values of the latent boils. At this stage, the liquid vapor pressure will equal the
heat of vaporization of ethanol were then obtained by using the
Clausius-Clapeyron equation, and the following Equations of
pressure inside the closed vessel, and its relationship with
State (EOS): van der Waals, Redlich-Kwong, and Soave- saturation temperature is shown by the Clausius-Clapeyron
Redlich-Kwong, which resulted to 6.088%, 4.583%, 4.198%, Equation. It can be derived from the fact that two phases
and 3.601% relative deviation, respectively. The Soave-Redlich- coexist in equilibrium during phase change, such that their
Kwong relation provided the most accurate value, as the molar Gibbs energy remains equal:
acentric factor, as well as the liquid volume, were taken into
consideration. 𝐺 𝛼 = 𝐺𝛽 Equation 2
Keywords: latent heat of vaporization; Ramsay-Young; Clausius-
Clapeyron; Equations of State; saturation temperature
where and represent two different phases. Furthermore,
since the two components are at equilibrium with one
another, the rates at which the Gibbs energies change will also
I. INTRODUCTION
be equal.
The Ramsay-Young Experiment, proposed in the
namesakes’ study, On a New Method of Determining the 𝑑𝐺 𝛼 = 𝑑𝐺𝛽 Equation 3
Vapour-pressures of Solids and Liquids, and on the Vapour-
pressure of Acetic Acid, investigates a method of ascertaining
the vapor pressure of liquids. This study involved the use of By applying the fundamental property
thermometer, Sprengel’s pump, and several laboratory
apparatuses that contained the acetic acid, which were sealed 𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 Equation 4
and kept air-tight to ensure that the measured temperatures and
pressures were kept constant throughout the experiment. The
saturation temperatures at varying pressures were also with Equation 2 and Equation 3, the following can be
determined (Ramsay & Young, 1862). obtained:
The system pressure is decreased by increments of 3 in- the actual boiling temperature. One of the challenges of this
glycerol, and the procedure was repeated until the pressure experiment was keeping the temperature and pressure reading
could no longer be decreased. stable since fluctuations are often caused by the presence of
air leaks in the experimental set-up.
III. RESULTS AND DISCUSSION
Through Figure 2, it can be seen that both experimental
The Ramsay-Young Method was utilized to determine the and theoretical boiling temperatures follow the same trend –
experimental boiling temperature of ethanol for the varying increasing pressure with increasing temperature. From the
pressures, as shown in Table 3. These pressures were also pressure vs. temperature plot, the experimental data have an
used to determine the theoretical boiling temperature through R2 of 0.991 when fitted to a linear trendline, suggesting that
the Antoine’s Equation. the boiling point increases linearly with temperature, as
predicted by the Antoine equation. The slope of the trendline
Table 3. Comparison of Experimental and Theoretical Boiling 𝑑𝑃 𝑠𝑎𝑡
for the experimental data, 𝑑𝑇 , is 4127.39 Pa/K and deviates
Temperatures of Ethanol
from the theoretical slope of 3887.52 Pa/K by 6.2%, which
Experimental Theoretical
Pressure Relative still suggests adequate agreement between the theoretical and
Temperature Temperature
(kPa)
(K) (K)
Error (%) experimental results.
93.256 343.55 349.27 1.639 The experimental boiling points are consistently lower
95.203 344.15 349.79 1.612 than the theoretical boiling points, with an average deviation
97.275 344.45 350.33 1.678 of around 1.60% or 5.77 K throughout all the trials. This
99.064 344.95 350.78 1.662 suggests that deviations from the predicted boiling points
101.326 345.55 351.31 1.650 based on Antoine’s equation are due to some systematic error.
The error may be due to the cooling of the ethanol vapor
Based on the data provided in Table 3, it can be observed before coming in contact with the thermocouple used to
that as the pressure of the system is increased, the record temperatures. Since the thermocouple was not
temperature, both for experimental and theoretical values, submerged in the solution, there were also likely convective
also increase. The experiment began at a low pressure setting heat losses in the region above the ethanol solution, which
of 93.256 kPa given that this was the pressure and lowered the recorded temperature by the thermocouple. There
temperature of the set up that was held stable for a period of may have also been leaks in the set-up as the manometer
time. Starting at a low pressure allows a trend in the reading fluctuate when the heating flask is moved. Leaks
temperature and pressure differences to be observed. Since from the heating flask would result to a lower actual pressure
the boiling points are lower at lower pressures, once a higher within the flask and would decrease the boiling point of the
pressure is set, the solution would stop boiling and more heat ethanol. This may not have been reflected in the manometer
would need to be added to increase the temperature to the new reading as it was directly connected to the condensing flask,
boiling point. If the experiment were performed starting from and not the heating flask where the ethanol was boiled.
high pressures, the solution would already be above the
boiling point once a new pressure is set, and will simply boil To obtain the latent heat of vaporization, a plot of lnP
1
more vigorously. This may increase the temperature readings versus 𝑇 was made, as shown in Figure 3.
obtained as the thermocouple and heating flask may be above
Figure 3. Plot of ln(P) vs. 1/T
The change in volume and latent heat of Based on the results, the Clausius-Clapeyron Equation
vaporization obtained for each equation of state is shown in yields the least accurate results, as the volume of the liquid is
Table 4. assumed to be negligible. In this case, only the volume of the
vapor is accounted for. The various Equations of State, on the
Table 4. Volume and Enthalpy Values for EOS
other hand, are more accurate and have a smaller relative
∆𝑽 (m3/mol) ∆𝑯 (kJ/mol) deviation because they account for liquid volume.
Trial
vdW RK SRK vdW RK SRK Furthermore, the Soave-Redlich-Kwong EOS has the
1 0.0302 0.0301 0.0299 42.802 42.650 42.412 smallest relative error of 3.601% because it takes into account
2 0.0296 0.0295 0.0293 42.063 41.911 41.674 the acentric factor, which is significant for ethanol as it is a
3 0.0290 0.0289 0.0287 41.226 41.074 40.838 polar molecule (ω = 0.645).
4 0.0285 0.0284 0.0282 40.589 40.438 40.203
5 0.0279 0.0278 0.0276 39.810 39.659 39.425
Average 41.298 41.146 40.911
Possible sources of error for this experiment include the
lack of a well-sealed/airtight/vacuum set-up. Having air leaks
in the system caused the pressure readings to heavily
fluctuate, thus making it difficult to measure the experimental
saturation temperatures of the system. In addition, because
the thermocouple was not in contact with the ethanol upon
measurement, it is possible that there are discrepancies in the
measured temperature which is another source of error in this
experiment.
ACKNOWLEDGEMENTS
Sample Calculations
*
!" # $%& = ( −
++-
/012.04
ln (93 256) = 16.8958 –
567/8.194
:+ =(+)
#= −
; − < (; + @<)(; + =<)
C +D :7 +E7
= + = B
#E
:+E
< = Ω
#E
# 93.256 Q 10/ #=
#D = = = 0.01516851
#E 6 148 000 #=
+ 343.55 R
+D = = = 0.66852
+E 513.9 R
ΩP^
\= = 0.002836231
+D
#C +D
_= = 5.048500946
Ω+D
`# $%&
→ b!cde cf # gb + = 4127.3942
`+
j `# $%&
hi = +∆; = 4127.3942 343.55 0.0301856
kc! `+
= mnopn. nqr J/mol
RK
9
@=0 Ω = 0.08664 B = 0.42748 Zc = 0.3333
C= +D7
# 93.256 Q 10/ #=
#D = = = 0.01516851
#E 6 148 000 #=
+ 343.55 R
+D = = = 0.66852
+E 513.9 R
9
C = 0.66852 7 = 1.22305
ΩP^
\= = 0.001965848
+D
#C +D
_= = 9.026727961
Ω+D
V (root) = 0.030138423
`# $%&
→ b!cde cf # gb + = 4127.3942
`+
j `# $%&
hi = +∆; = 4127.3942 343.55 0.030138423
kc! `+
= mn smt. umt J/mol
SRK
CvUw = @ Ω B Zc = x
7
1 + 0.480 + 1.574x − 0.176x7 = 0 = 0.08664 = 0.42748 0.333 = 0.645
∙ (1 − +D.2 ) 3
# 93.256 Q 10/ #=
#D = = = 0.01516851
#E 6 148 000 #=
+ 343.55 R
+D = = = 0.66852
+E 513.9 R
7
1 + 0.480 + 1.574x − 0.176x7
CvUw = = 1.58592
∙ (1 − +D.2 )
ΩP^
\= = 0.001965848
+D
#C +D
_= = 11.70492267
Ω+D
V (root) = 0.029971207
`# $%&
→ b!cde cf # gb + = 4127.3942
`+
j `# $%&
hi = +∆; = 4127.3942 343.55 0.0299108
kc! `+
= mn mqn. mmq J/mol
= s. pooqopnÅm%