HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY

 

PHYSICAL CHEMISTRY EXPERIMENT REPORT

Lecture 1

LIQUID-VAPOUR EQUILIBRIUM

Class: CC03

Group: 4

Date: 19/09/2021

Instructor: PGS.TS Nguyễn Trường Sơn

Members ID Điểm số

Nguyễn Ngọc Bảo Trân 1952504

Tô Phan Phương Trang 1850052

Trần Quốc Trung 1953053

Đặng Quốc Tuệ 1952519

 CONTENT

I. THEORY.................................................................................................................................3

II. EXPERIMENTS.................................................................................................................8

1. Equipments - Chemicals.....................................................................................................8

2. Progress...............................................................................................................................8

III. RESULT............................................................................................................................10

I.

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I. THEORY
1. Definition of Ideal solution

Ideal solution is described as a homogeneous solution where the interaction

between molecules of components (solute and solvents) is exactly the same to the
interactions between the molecules of each component itself. Such as Benzene and
Toluene, Ethyl Iodide and Ethyl Bromide, Bromobenzene and Chlorobenzene, n-
heptane and n-hexane.

Assume that the solution has 2 completely miscible liquids A and B, which is in
equilibrium with vapor phase containing 2 components A and B. With ideal solution,
we can apply Raoult’s Law to determine composition of vapor A and B.

2. From extracting the measured solution samples. Determine the concentration

of the solution
By using the calibration curve method
First mix the solutions of the correct composition, measure the refractive index
of the solution to form a curve n=f(x).
Then use this calibration curve to determine the composition of the solutions
when its refractive index is known.
(Use the data for making the calibration curve has been provided by the
laboratory to draw the standard curve)
3. Raoult's law and Konovalov’s first law

Raoult's law

Raoult's law states that the vapor pressure of a solvent above a solution is equal to
the vapor pressure of the pure solvent at the same temperature scaled by the mole
fraction of the solvent present. At any given temperature for a particular solid or
liquid, there is a pressure at which the vapor formed above the substance is in
dynamic equilibrium with its liquid or solid form. At equilibrium, the rate at which
the solid or liquid evaporates is equal to the rate that the gas is condensing.

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 Psolution =X solvent × Posolvent

Positive and negative deviation

Positive deviation Negative deviation

 Vapor pressure of solution and  Vapor

partial pressure of the components pressure of solution and partial
are more than those expected by pressure of the components are less
Raoult’s law. than those expected by Raoult’s law.
 ∆ H mix ≠ 0 and it is positive  ∆ H mix ≠ 0 and it is negative

 ∆ V mix =¿ positive  ∆ V mix =¿ negative

 Form minimum boiling azeotrope  Form maximum boiling azeotrope
 On mixing intramolecular attraction  On mixing intramolecular attraction
decreases (CH3COCH3 + CS2) increases (CH3COCH3 + CHCl3)

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 Konovalov’s first law

Konovalov’s first law states that at identical temperature conditions the total
saturated vapor pressure of a solution rises with an increase in the concentration of
that component whose content is greater in the vapor than in the solution and
decreases with an increase in the concentration of that component whose content is
lower in the vapor than in the solution.

x hB P0B x lB x lB
= × =α
xhA P0A x lA x lA

P0B
α = 0 : separation coefficient/ distillation coefficient
PA

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4. Determine the composition of the vapor phase in equilibrium with the liquid
phase
Ideal solution (homogenous mixture): use Raoult’s law or Konovalov’s first law
Real solution: because of the negative and positive deviation of Raoult’s law, the
laws above are inaccurate, we need to determine experimentally.
5. In this experiment, why we just need to take 3 to 5 drops of steam condensate
to extract
If we take a small number of drops, then it is not enough to measure. By contrast,
the composition of the liquid phase remaining in the distillation flask will be
significantly altered and also change the boiling point. Hence, it is necessary to
measure the temperature before and after take a drop of steam.

6. Definition of Azeotrope, Azeotropic point and its application

Azeotrope is a liquid mixture that has a constant boiling point and whose vapor
has the same composition as the liquid.

If we illustrate the dependence of vapor pressure on composition of liquid phase

and vapor phase on the same diagram then two graphs will intersect at the extremum.

Maximum on P-x while minimum on T-x.

Azeotropes are used as standards in testing gas chromatographs, detectors, and

columns. They are used for the separation of constituents of zeotropic mixtures. For
example, it is very difficult to separate pure acetic acid from a solution of acetic acid
and water. As we know, ethyl acetate forms an azeotrope with water and boils at

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70.4℃. So, by adding ethyl acetate in the mixture of acetic acid and water as an
entrainer (solvent), it is possible to distill away the azeotrope (ethyl acetate and water)
and leave nearly pure acetic acid in the distillation flask. As boiling point of acetic
acid is 118.1℃.

7. Why we need to put pumice stone in during experimental distillation

The pieces of pumice stone are added to before heating to avoid bumping of
liquid when the temperature rises. When water boils it releases energy in the form of
bubbles. Moreover, if the bubbles are not formed, then the water will superheat and
can possibly explode. So, the main purpose of adding pumice stone is to facilitate the
formation of bubbles so that “Bumping” can be prevented. It frequently happens,
especially when the distillation has to be carried out under greatly reduced pressure,
and that the liquid is liable to boil with bumping and thus we are able to measure the
boiling point of water more accurately. Adding pieces of rough stone gives lots of
surface area for bubbles to form and release the energy gradually.
Pumice is usually aluminum oxide, calcium carbonate, or silica minerals with
many pores, rough surfaces, thus creating many boiling points. The pumice stone
must be inert in the working solvent environment.

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 Note: Put pumice into the flask before heating, if it is hot, the solvent may boil
violently and spill out, possibly exploding. Only used once

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II. EXPERIMENTS
1. Equipments - Chemicals

Equipments - Chemicals Quantity

Distillation Apparatus 1
Filter paper 1
Glass rod 1
Alcohol thermometer 100oC 1
Electric stove 1
Cover 1
Small glass bottle 1
Becher 250ml 1
Refractometer 1
Chloroform - Acetone 6 (bottles)

2. Progress
Step 1
- Using pipette (or burette) to take different compositions of chloroform –
acetone into 6 flasks.
- Close the septum stoppers, shake well.
- Using the refractometer to obtain the refractive index of pure components
and solutions
- Report the data into the table 1.

Step 2

(Distillation apparatus)

- Pouring one solution with corresponding composition into the flask (1)
(about 2/3 volume of the flask). Put some pumices into the flask.

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- Resemble the distillation apparatus, please note that we should keep the
part containing alcohol of thermometer into at least half of the solution
inside to avoid the error in the process. Let water flow through condenser.
- Heat up the heater until it boils at stable state. Record the boiling
temperature T 1
- Turn the condenser towards the beaker (5). Take 3-5 drops of condensed
vapor into the beaker then close the lid tightly. Continue using the
refractometer to get the refractive index value of the condensed vapor.
- Turn the condenser upward and record boiling temperature T 2. If the
deviation between T 1 and T 2 exceeds 1o C , we have to set up again.
T 1 +T 2
- T average=
2
- Repeat those steps with the following solutions.

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 III. RESULT
After completing the table below, we can construct the phase diagram of this
solution by illustrating the relationship between boiling temperature and composition
of condensed vapor phase and liquid phase.

Density of Chloroform (g/cm3) 1.483 M (g/mol) 119.38

Density of Acetone (g/cm3) 0.7905 M (g/mol) 58
Table 1
Refractiv 1.44 1.383
1.433 1.4254 1.4175 1.4099 1.4013 1.3929 1.3739 1.3
e index 2 4
%Vol of
0 10 20 30 40 50 60 70 80 9
Acetone
Mol
fraction 0.3198 0.4224 0.5231 0.6220 0.719 0.8144 0.9
0 0.108659 0.21524707
of 2 4 6 3 1 2 4
Acetone

 Assume that we use 100 ml of solution.

 Mol fraction of Acetone:

V acetone × Dacetone
nacetone M acetone
=
nacetone +n chloroform V acetone × Dacetone (100−V ¿¿ acetone)× Dchloroform
+ ¿
M acetone M chloroform

Table 2

No. 1 2 3 4 5 6
1.392 1.405 1.405 1.422
Liquid 1.3761 1.4303
Refractive index 3 0 0 4
(n) 1.384 1.402 1.419 1.425
Vapor 1.3644 1.4307
1 0 7 4
Before taking
60 62 63 61 61.5 61
Boiling sample
temperature (oC) After taking
60 62.5 63.5 61 62 61.5
sample

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 T 1 +T 2
T average=
2

Temp
60 62 63 61 61.5 61
before
Boiling temperature(oC) Temp after 60 62.5 63.5 61 62 61.5
Temp
60 62.25 63.25 61 61.75 61.25
average

We have the equation above: y = -0.0852x + 1.4439

Substitute y by refractive index then find the value of x:

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