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Determination of the Latent Heat of Vaporization of

Ethanol through the Ramsay-Young Method


Alvarillo, Camille Margaret1, Buensuceso, Maria Crispina1, Gonzales, Ysabel Marie1, Uy, Jaron Nicolas1
1
Department of Chemical Engineering, University of the Philippines – Diliman
Quezon City, Philippines

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:

In obtaining the theoretical boiling temperatures of the


𝑉 𝛼 𝑑𝑃 − 𝑆 𝛼 𝑑𝑇 = 𝑉𝛽 𝑑𝑃 − 𝑆𝛽 𝑑𝑇 Equation 5
substance at different pressures, the Antoine Equation was
used:
The equation can further be rearranged to obtain Equation 6.
𝐵 Equation 1
𝑙𝑛(𝑃 𝑠𝑎𝑡 ) = 𝐴 −
𝑇+𝐶
𝑑𝑃 𝑆𝛽 − 𝑆 𝛼 ∆𝑆 Equation 6
For pure ethanol, the Antoine’s constants (Smith, Van Ness, = =
& Abbott, 2005) are found in Table 1. 𝑑𝑇 𝑉𝛽 − 𝑉 𝛼 ∆𝑉

Table 1. Antoine’s Coefficients for Pure Ethanol (kPa, °C)


A 16.8958 By applying the Second Law of Thermodynamics to Equation
B 3795.78 6, Equation 7 can be obtained.
C 230.918
𝑑𝑃 ∆𝐻 Equation 7
=
In a confined space where vapor to liquid phase change is 𝑑𝑇 𝑇∆𝑉
expected to happen, molecules will move from the vapor
For the Clausius-Clapeyron Equation, the volume of the
vapor is assumed to be significantly larger than that of the Other parameters for the different equations of state used
liquid, which can be expressed as are shown in Table 2.

Table 2. Parameters for the Equations of State


𝑅𝑇 Equation 8 EoS Zc
∆𝑉𝑙𝑣 = ∆𝑉𝑔 = 𝑠𝑎𝑡
𝑃 VdW 1 0 0 1/8 27/64 3/8
RK 𝑇𝑟−.5 1 0 0.08664 0.42748 1/3
Lastly, substituting Equation 8 into Equation 7 will result to SRK 1 0 0.08664 0.42748 1/3
SRK

𝑑𝑃 𝑃 𝑠𝑎𝑡 ∆𝐻 Equation 9 𝛼𝑆𝑅𝐾 = Equation 12


=
𝑑𝑇 𝑅𝑇 2 1+ (0.480 + 1.574𝜔 − 0.176𝜔2 )
2
( )
Integrating this, the working Clausius-Clapeyron Equation ∙ (1 − 𝑇𝑟.5 )
can be obtained.
where is the acentric factor
𝑠𝑎𝑡
∆𝐻 Equation 10
𝑙𝑛(𝑃 )=
𝑅𝑇
Through the Ramsay-Young method, the study aims to
where P is the saturation pressure experimentally determine the latent heat of vaporization of
T is the saturation temperature ethanol through the method’s application, as well as the use
R is the gas constant of the Clausius-Clapeyron Equation, van der Waals, Redlich-
H is the latent heat of vaporization of pure liquid Kwong and Soave-Redlich-Kwong equations of state.
Furthermore, this study also aims to compare the
The Clausius-Clapeyron Equation relates the pressure and experimental data from the various equations used and the
saturation temperature to the latent heat of vaporization. The literature values of the latent heat of vaporization of ethanol.
latent heat is essentially the heat effect that accompanies
phase change that occurs at a constant temperature. It can be
1
determined by plotting lnP vs. 𝑇 and performing linear II. MATERIALS AND METHODOLOGY
regression.

In lieu of the Clapeyron Equation, equations of state


(EOS), namely the van der Waals, Redlich-Kwong and
Soave-Redlich-Kwong may also be used to obtain the change
in volume, V, associated with the phase change. This will
allow the direct use of Equation 7 to calculate for the latent
heat of vaporization without the simplifying assumption that
the volume of the vapor is significantly larger than that of the
liquid. The latent heat of vaporization may then be calculated
using the changes in volume predicted by each equation of Figure 1. Setup of Ramsay-Young Experiment (“Chemical Engineering
state.The equations of state to be used are all in the form in Thermodynamics Laboratory Manual,” 2013)
Equation 11 obtained from Smith et al. (2005).
The setup for the Ramsay-Young Method was
prepared as shown in Figure 1.
𝑅𝑇 𝑎(𝑇) Equation 11
𝑃= − In the setup, a vertical flask is closed at the top by
𝑉 − 𝑏 (𝑉 + 𝜀𝑏)(𝑉 + 𝑎𝑏)
an accurately fitting cork perforated with a hole for a
thermocouple probe to pass. Rubber tubing connects this
where P is the pressure of the system flask to another flask, which is immersed in an ice bath. This
T is the temperature of the system second flask is connected to a vacuum pump and to a
V is the volume occupied by the system manometer, which is controlled by a manometer valve.
𝛼(𝑇𝑟 )𝑅2 𝑇𝑐2
𝑎(𝑇) = 𝜓 Once the vacuum pump and manometer valve were turned
𝑃𝑐 on, a constant pressure reading on the manometer was
𝑅𝑇𝑐 obtained. The theoretical saturation pressure of ethanol was
𝑏= Ω
𝑃𝑐 then obtained using this pressure through the Antoine
R is the gas constant Equation. The temperature of the hot plate was then adjusted
Tc is the critical temperature a few degrees above the theoretical saturation temperature.
Tr is the reduced temperature Then, once the temperature reading of ethanol was constant,
Pc is the critical pressure it was recorded.
Figure 2. Saturation Pressure vs. Temperature

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

∆𝐻 It may be seen that the different equations of state


Based on Equation 10, the slope of this graph is 𝑅 , so the
give different results for the change in volume associated
latent heat of vaporization may be obtained by multiplying
with the phase change, and give different latent heats. These
the slope by the gas constant, R. The experimental latent heat
are due to the different assumptions with each equation of
of vaporization obtained is 41.893 kJ/mol, which deviates
state. The van der Waals equation of state is the simplest and
from the theoretical value of 39.488 kJ/mol (Dong, Lin, &
takes into account the volume of the particles, and the effect
Yen, 1988) by 6.088%. The R2 of the plot is 0.9899, which
of inter-particle attractions on the pressure. The Redlich-
suggests a good linear fit of the data to the theoretical model.
Kwong equation of state improved on the van der Waals
equation and accounted for the temperature dependence of
Alternatively, the latent heat of vaporization was also
the attraction parameter suggested by van der Waals (Craig,
calculated using the van der Waal (vdW), Redlich-Kwong
2000). Finally, the Soave-Redlich-Kwong equation takes into
(RK), and Soave-Redlich-Kwong (SRK) equations of state.
account the shape of the molecule through the acentric factor.
These were used to obtain the volume of the liquid and vapor,
from which the change in volume may be obtained. This was Table 5. Comparison of Enthalpy Values Obtained through Clausius-
then used with the Clapeyron equation, shown in Equation 7, Clapeyron, Van der Waals, Redlich-Kwong, and Soave-Redlich-Kwong
to calculate for the latent heat of vaporization. The rearranged Equations
version of the equation is: Experimental Theoretical
Relative
Equation Enthalpy Enthalpy
Error (%)
𝑑𝑃 𝑠𝑎𝑡 Equation 13 (kJ/mol) (kJ/mol)
∆𝐻 = 𝑇∆𝑉
𝑑𝑇
Clapeyron 41.893 6.088
where 𝑑𝑃 𝑠𝑎𝑡 vdW 41.298 4.583
is the slope of Figure 2, previously obtained 39.488
𝑑𝑇 RK 41.146 4.198
to be 4127.39 Pa/K SRK 40.911 3.601

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.

IV. CONCLUSIONS AND RECOMMENDATIONS

The objective of this experiment is to determine the latent


heat of vaporization of ethanol using the Ramsay-Young
method, and through the applications of the Clausius-
Clapeyron equation and the van der Waals, Redlich-Kwong
and Soave-Redlich-Kwong equations of state. Among the 4
equations used, the Soave- Redlich-Kwong provided the most
accurate latent heat of vaporization with a 3.601% relative
deviation from the theoretical value. This was because it
accounted for the polarity of ethanol which decreased
deviation from literature value. In this experiment, it was also
observed that as the system pressure is increased, the
saturation temperature of ethanol also increased. This was a
consistent observation for both the experimental and
theoretical data provided in this study.

The objectives of this experiment can be explored further


by performing an alternative method such as calorimetry to
determine the latent heat of vaporization of substances of
interest. This experiment can be improved by performing an
alternative method such as calorimetry to determine the latent
heat of vaporization of compounds of interest. Moreover,
more accurate data can still be obtained if the sources of error
were mitigating. This can be done by assuring that the
Ramsay-Young set-up is well sealed. Perhaps, instead of
using masking tape to seal the set-up, more rubber stoppers
that completely seal the cover of the flasks may be used to
avoid air leaks. Lastly, a longer thermocouple that can come
in contact with the ethanol solution may be used to avoid
discrepancies in temperature measurement.

ACKNOWLEDGEMENTS

We would like to thank Engr. Myron Alcanzare of the


Department of Chemical Engineering for his invaluable input
and never-ending support that led towards the success of this
study.
REFERENCES
[1] Chemical Engineering Thermodynamics Laboratory Manual. (2013), 1,
45.
[2] Craig, N. C. (2000). Molecular Thermodynamics (McQuarrie, Donald A.;
Simon, John D.). Journal of Chemical Education, 77(1), 31.
https://doi.org/10.1021/ed077p31.2
[3] Dong, J.-Q., Lin, R.-S., & Yen, W.-H. (1988). Heats of vaporization and
gaseous molar heat capacities of ethanol and the binary mixture of
ethanol and benzene. Canadian Journal of Chemistry, 66(4), 783–
790. https://doi.org/10.1139/v88-136
[4] Ramsay, W., & Young, S. (1862). On a New Method of Determining the
Vapour-pressures of Solids and Liquids, and on the Vapour-pressure
of Acetic Acid. Journal of the Chemical Society, (42), 42–45.
[5] Smith, J. M., Van Ness, H. C., & Abbott, M. M. (2005). Introduction to
Chemical Engineering Thermodynamics. Chemical Engineering
(Vol. 27). https://doi.org/10.1021/ed027p584.3
Appendix

Sample Calculations

For obtaining boiling temperatures using Antoine Equation

*
!" # $%& = ( −
++-
/012.04
ln (93 256) = 16.8958 –
567/8.194

Solving for T = 349.27337 K

Equations of State: For Trial 1

:+ =(+)
#= −
; − < (; + @<)(; + =<)

C +D :7 +E7
= + = B
#E

:+E
< = Ω
#E

Van der Waals

C=1 @=0 Ω = 0.125 B = 0.421875 Zc = 0.375

# 93.256 Q 10/ #=
#D = = = 0.01516851
#E 6 148 000 #=

+ 343.55 R
+D = = = 0.66852
+E 513.9 R

S 5T U V 5WV 8.Y79402 4./9YV 29/.1V


a(T) = B = = 1.252642686
XW Z 9Y4 888 X%

:+E 0.125 8.314 513.9 R


< = Ω = = 8.6869 Q 10[2
#E 6 148 000 #=

ΩP^
\= = 0.002836231
+D
#C +D
_= = 5.048500946
Ω+D

8.314 343.55 R 1.252642686


93.256 Q 10/ = −
; − 8.6869 Q 10[2 ; ; + 1.252642686 8.6869 Q 10[2
V (root) = 0.030272754

`# $%&
→ 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

S 5T U V 5WV 8.Y70Y4 (9.77/82) 4./9YV 29/.1V


a(T) = B = = 1.5523997
XW Z 9Y4 888 X%

:+E 0.08664 8.314 513.9 R


< = Ω = = 6.02106 Q 10[2
#E 6 148 000 #=

ΩP^
\= = 0.001965848
+D
#C +D
_= = 9.026727961
Ω+D

8.314 343.55 R 1.5523997


93.256 Q 10/ = [2

; − 6.02106 Q 10 ; ; + 1.5523997 6.02106 Q 10[2

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 )

S 5T U V 5WV 8.Y70Y4 (9.24217) 4./9YV 29/.1V


a(T) = B = = 2.012990589
XW Z 9Y4 888 X%

:+E 0.08664 8.314 513.9 R


< = Ω = = 6.02106 Q 10[2
#E 6 148 000 #=

ΩP^
\= = 0.001965848
+D
#C +D
_= = 11.70492267
Ω+D

8.314 343.55 R 2.012990589


93.256 Q 10/ = [2

; − 6.02106 Q 10 ; ; + 2.012990589 6.02106 Q 10[2

V (root) = 0.029971207

`# $%&
→ b!cde cf # gb + = 4127.3942
`+

j `# $%&
hi = +∆; = 4127.3942 343.55 0.0299108
kc! `+
= mn mqn. mmq J/mol

Calculating for % error:

|ℎec{e|~=! − =|Ä=! 39.4884792 − 41.892609


% e{{c{ = = Q 100%
|ℎec{e|~=! 39.4884792

= s. pooqopnÅm%