Construction of the Clausius - Clapeyron equation by measuring the

saturated vapor pressure of an acetone solution.

Abstract
The saturated vapour pressure of acetone was measured by using Smith and
Menzies’ method at different temperatures from 304K to 311K. From the
experimental values, the Clausius - Clapeyron equation was established in order
to calculate the saturated vapour pressures at a given temperature. By applying
the values of the ambient pressure into the Clausius - Clapeyron equation, the
normal boiling temperature of the acetone was calculated is . This temperature is
close to the accepted value. Smith and Menzies’ method was considered to be
the correct method for measurement the saturated vapor pressure of the acetone
solution.
Introduction
The pressure at which a vapour phae is in thermodynamic equilibrium with its
liquid or solid phase is defined as the saturated vapour pressure. The liquid
reaches its boiling point when the vapor pressure equals the external
atmospheric pressure. A liquid's boiling point is the temperature at which its
equilibrium vapor pressure equals the pressure exerted on it by its gaseous
surroundings. This pressure is due to the earth's atmosphere for liquids in open
containers. This temperature represents the heat of phase transition from a liquid
or solid to a gas.
The condensation and vaporization, two opposing processes, occurs
simultaneously at the liquid's surface. As being illustrated in Figure 1, when a
volatile liquid is placed in a closed vessel, at the beginning, the evaporation rate
is greater than the condensation rate as more molecules gets out of the liquid
surface. The rate of aforementioned processes will get higher condensation and
lower evaporation, respectively, over time. The rate of evaporation reaches its
maximum after a trade. As the rate of condensation accelerates, liquid-vapour
equilibrium will be reached the point which both processes share the same rate.
In details, when the surface evaporation is not changed, molecules from the
liquid phase will continuously leave from the liquid's surface, but this time they
are kept water surface above the liquid. Some of the molecules of the vapour
phase will come back the liquid's surface and then are trapped there. An
equilibrium will reach as the number of molecules leaving the surface is equal
with the number of molecules come back to the liquid phase. The amount of
molecules form the vapour in the area above the liquid will fixed. The pressure
was resulted when these molecules collide with the container's walls. The
saturated vapour pressure of the liquid (also referred to as saturated vapour
pressure) is the term used to describe this pressure.

Figure 1. Evaporation and condensation.

According to the Clausius- Clapeyron equation, the vapour pressure is a function
of temperature:
(Eq.1)
Where P is the saturated vapour pressure, T is the temperature, is the heat of
evaporation and R is the ideal gas constant.
If the region of interest temperature range is small, then is considered assumed,
transform Eq.1, and could be rewritten the unidentified integral. can be
considered as a linear function of using Eq.2.
(Eq.2)

Figure 2. Graph of in the Clausius - Clapeyron equation.

In order to determine the value of , the vapour pressure will be measured as
various condition, temperature ranges. Then base on the graph of to find as
follows:
(Eq.3)
Where and .
Here are the way of calculating the values for and . Firstly, by applying these
values in Eq.2, B can be determined. When a liquid's vapour pressure reaches
atmospheric pressure, that temperature is considered to be the boiling point of
that liquid. If P is 760 mmHg, Ts will be calculated as follows from Eq.2:
.
A device known as Isoteniscope is used in one method described by Smith and
Menzies. A peach jar about 3 cm in diameter is half-filled with the experimental
liquid, which is then introduced into the tube's two limbs. The Isoteniscope is
immersed in a constant temperature bath and linked to a vacuum pump. In the
apparatus, there is a manometer, M, and a large bottle, C, for pressure
regulation. Smith and Menzies' method for measuring vapour pressure was used
in this experiment, and the measurement apparatus is depicted in figure 3.

Figure 3. Saturated vapour pressure measurement apparatus

Methodology
Connect the peach jar to the N-tube after the acetone solution was added into
branches A and B and the peach jar (about 2/3 volume). Put the jar in the water.
It must be immersed in water, as illustrated in Figure 1.3.
All of the air from A had been removed in the following manner: Maintaining the
thermostat at the temperature to be measured t. The vacuum pump was stared
and the valve J was gradually opened. The gas pressure in the stabilizer C
dropped, raising the liquid levels at B2 and M while decreasing at B1 and L. the
air inside A was let out along with the gas bubbles.
After removing all of the air from A, the valve J was closed. Then, the valve K
was slowly opened to let air in until the liquid levels at B1 and B2 were equal, and
then the valve K was closed instantaneously. Then, all of values of the
temperature t, atmospheric pressure H, and pressure difference h were recorded.
The thermostat's temperature was raised (1–1.5° C), after which P was
measured at corresponding temperatures. the pressure 6-8 values of P was
determined.
Results
The values was summarized in table 1 in order to create a graph of for
determining λ, B, Ts and establishing the Clapeyron-Clausius equation. All of the
measuring experiment's specific data were shown in Table 1.
Table 1. The experimental data of measuring P at temperature ranging from
304K to 311K

T (K) 304 305 306 307 308 309 310 311

1/T 3.289 2.279 3.268 3.257 3.247 3.236 3.226 3.215
h 447 437 425 414 400 386 370 357
P 313 323 335 346 360 374 390 403
lnP 5.746 5.778 5.814 5.846 5.886 5.924 5.966 5.999

The relationship between the saturated vapour pressure and the temperature is
shown in Figure 3.

Figure 3. Graph of lnP = f(1/T)

As being depicted in Figure 2, the graph resembles a linear line with a negative
slope and fits with a trendline y = -3.4678x + 17.148 with a squared value on
chart is 0.9983. The values of the two points at M(3.229,5.95) and N(3.287,.75)
were used for further calculation, in details:

The Clausius – Clapeyron equation was determined as follows:

Moreover the enthalpy of vaporization which was calculated by Eq.3 is 28869

J/mole and the normal boiling temperature of the acetone is .
Discussion
The Table 1 shows an overview of the relationship between the saturated vapour
pressure and the temperature. In this experiment, when the temperature
increases from 31 to 38 degrees, saturated vapor pressure is proportional to the
temperature. The saturated vapour pressure rises and so does the temperature,
and vice versa. This is consistent with the established Claysius - Clapeyron
equation.
Effect of the temperature on the Heat of evaporation based on the Kirchhoff's
law:

where . Because is quite small in comparison to the value of . Moreover, given

that the heat capacity of a vapour state is typically around 2/3 that of a liquid
state according to experimental data. So that, the value of is extremely low.
Therefore, within a limited temperature range, heat of evaporation does not
depend on the temperature.
Pseudo-experimental value obtained from the NIST Chemistry Web-book is
taken, which are conveniently available for acetone. The calculated normal
boiling temperature of the liquid in the experiment is very close to the accepted
value (the boiling temperature of acetone shown on NIST Chemistry Web-book I
56 degree Celsius). This difference can be explained by some experimental
errors. In this experiment, possible sources of error include: the air was not
removed completely from A and the acetone levels in B1 and B2 are not equal.
Firstly, if the air was still above A, the measured pressure p is greater than the
actual pressure acetone, resulting in a positive error in the measurement result.
Secondly, if the acetone levels in B1 and B2 was quite different like 1 centimeter,
actual pressure and measured pressure are separated by 0.57mmHg. To reduce
these errors, the steps in the experimental process must be carefully followed
and repeated several times.
Conclusion
In this experiment, the Clausius - Clapeyron equation was established based on
measuring the saturated vapour pressure. The graph showing the relationship
between saturated vapour pressure and the temperature form a linear line with a
negative slope The enthalpy of vaporization which was calculated is 28869
J/mole and the boiling point of acetone at . During the experiment, occurred
errors include the air was not removed completely from A and the acetone levels
in B1 and B2 are not equal. Repeating the experiment in order to measure better
data and minimize these errors.
References
i