Establishment of the Clausius-Clapeyron equation using the method

of measuring the saturated vapor pressure

Student’s Name: Hoang Ngoc Hoan

Student ID: 20201500

Class ID: 146013

Instructor: Vu Thi Ngoc Minh

Date of submission: 05/12/2023

Introduction

The saturated vapor pressure of a liquid represents the equilibrium pressure of

its vapor above the liquid or solid phase, dependent on temperature.[1] The
experiment aims to derive the Clausius-Clapeyron equation by measuring the
saturated vapor pressure of a volatile liquid at various temperatures. Utilizing
pressure-temperature data and the Clausius-Clapeyron equation, the experiment
allows for the determination of the heat of vaporization and boiling point of the
liquid.[1]
A vapour in thermodynamic equilibrium with a liquid causes pressure called the
liquid’s equilibrium vapor pressure. At the surface of the liquid, two opposing
processes always occur: evaporation and condensation. When the experiment is
taken place in a closed container, the rate of evaporation is greater than the rate of
condensation; however, after a period of time, they are equal because the
evaporation’s rate does not change and the condensation’s rate increases gradually.
[1]
 Figure 1. Vaporization and condensation of a liquid

As the Clausius-Clapeyron equation, the equilibrium vapor pressure (P) of a

liquid varies with temperature (T):
d lnP ¿ λ
dT 2 (1)
RT
With: -P: The saturated vapor pressure
-T: Temperature (K)
- λ : Enthalpy of vaporization
-R: Ideal gas constant
In a relatively confined temperature range, assuming λ is constant,
integrating the equation yields:
−λ A
lnP = 2 + const = +B (2)
RT T

By measuring pressure at multiple temperatures within this narrow range

and plotting the lnP = f(1/T). From the graph lnP = f(1/T),
-A = tg α
λ
And A= R

Therefore: λ = A.R = - R.tgα

Tgα is determined from the coordinates of two points M and N on the line lnP =
f(1/T) in figure 2:
∆y y
M −¿ y
tgα = ∆ x = x ¿N

M −¿ x ¿
N
 Figure 2. the graph lnP = f(1/T)

With one value of lnP substituted into equation (2), one value of the integral
constant B will be determined.
If the pressure is measured at a temperature near the boiling point, equation
(2) can be used to calculate TS. with pressure P measured in mmHg:
−A
ln 760 = 6,6333 = T + B
s

Methodology

Among a lot of methods of measuring the saturated vapor pressure, Smith

and Menzies’ method is used.
 Figure 3. Diagram of the apparatus used for measuring the saturated vapor pressure

1. Acetone was put into two branches A,B of the peach vase (about 2/3 full) and
then was connected to tube N. The flask was dipped into a beaker of water in
the thermostat (the flask must be submerged in water). [1]
2. Removing all the air above the liquid at A.
The thermostat was set to the target temperature for measurement. The suction
pump was activated, and valve J was gradually opened. As the gas pressure in
vessel C decreased, liquids B2 and M rose, while B1 and L lowered. Air bubbles
from A emerged, removing air. Valve J was fine-tuned to maintain uniform bubble
velocity, preventing liquid overflow into jar C. Air was drawn for 30-60 seconds.
After closing valve J, valve K was slowly opened to equalize levels B1 and B2;
then, valve K was closed. Measurements of temperature (t), atmospheric pressure
(H), and differential pressure (h) were recorded. The process was repeated,
maintaining temperature at t0, until h values at consecutive times remained
constant, indicating complete air expulsion above A.
3. The method of measuring the acetone saturation pressure at various
temperatures.
No further air expulsion was required in the second measurement, as the air
above A had been expelled. The vacuum pump was switched off. Saturation
pressure of acetone was measured at various temperatures by gradually increasing
the thermostat temperature (approximately 1-1.5°C each time). After stabilizing the
temperature at t for measurement, h was measured by slowly opening valve K to
equalize levels B1 and B2, then closing valve K. This process was repeated for
around 6-8 different temperature values. Using the measured h value, P was
calculated using the formula:
PA = H – h

Results

Figure 4. The graph lnP = f(1/T)

The chart featured a logarithmic base e scale on the x-axis, representing the
measured saturated vapor pressure (P). Meanwhile, the y-axis depicted the
reciprocal of temperature (T).

Discussion

From Table 1, the data was calculated according to the following formula:
∆y yM −¿ y 5 , 96−5 , 81
tgα = ∆ x = x ¿=
N
= -3750
M −¿ x ¿
N
( 3 ,22−3 ,26 ) .10−3

So, the Clausius-Clapeyron equation found was:

 −3750
lnP = + 18,02
T

The graph illustrates that lnP was a first-order function of 1/T, with the percentage
error consistently low. The alignment between theory and reality was notably
close, suggesting a lack of significant differences. Factors influencing the results
may stem from either chemical purity or laboratory procedures. To mitigate errors,
employing a meticulously prepared standard solution and ensuring precise
determination of temperature and pressure are recommended solutions.

Conclusion

The pressure exerted by a vapor in thermodynamic equilibrium with a liquid is

known as the liquid's equilibrium vapor pressure. The Clausius-Clapeyron equation
temperatures were determined through the method of measuring the saturated
vapor pressure of a volatile liquid at different temperatures. Utilizing pressure‐
temperature data and the Clausius‐Clapeyron equation, one can deduce the heat of
vaporization and boiling point for the liquid.

References

[1] Bo mon Hoa ly, Tai lieu thi nghiem Hoa ly 1 [General Chemistry laboratory
manual], (in Vietnamese). Nha xuat ban Bach Khoa Ha Noi, 2019.

Appendix

Table 1. Experimental data sheet

toC 32 33 34 35 36 37 38
T 305 306 307 308 309 310 311
1/T (x10-3 ) 3,28 3,27 3,26 3,25 3,24 3,23 3,22

H(mmHg) 456 439 427 414 400 386 373

P(mmHg)=H-h 304 321 333 346 360 374 387
lnP 5,72 5,77 5,81 5,85 5,89 5,92 5,96