Latent Heat of Vaporization

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Latent Heat of Vaporization

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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:

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

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.

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

=

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.

(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

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.

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.

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

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

*

!" # $%& = ( −

++-

/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

a(T) = B = = 1.252642686

XW Z 9Y4 888 X%

< = Ω = = 8.6869 Q 10[2

#E 6 148 000 #=

ΩP^

\= = 0.002836231

+D

#C +D

_= = 5.048500946

Ω+D

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

a(T) = B = = 1.5523997

XW Z 9Y4 888 X%

< = Ω = = 6.02106 Q 10[2

#E 6 148 000 #=

ΩP^

\= = 0.001965848

+D

#C +D

_= = 9.026727961

Ω+D

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 )

a(T) = B = = 2.012990589

XW Z 9Y4 888 X%

< = Ω = = 6.02106 Q 10[2

#E 6 148 000 #=

ΩP^

\= = 0.001965848

+D

#C +D

_= = 11.70492267

Ω+D

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

% e{{c{ = = Q 100%

|ℎec{e|~=! 39.4884792

= s. pooqopnÅm%

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