HANOI UNIVERSITY OF SCIENCE AND TECHNOLOGY

SCHOOL OF CHEMICAL ENGINEERING

DEPARTMENT OF PHYSICAL CHEMISTRY
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Experimental Physical Chemistry

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Manuals

Experiments of Physical Chemistry

(CH3082E and CH3007E)
(For the Advanced program in Technology of Pharmaceutical
chemistry)

© Dept. Physical Chemistry, 1/2023

EXPERIMENT 1: SATURATED VAPOUR PRESSURE ....................................................... 2
EXPERIMENT 2: DISTRIBUTION LAW ............................................................................... 7
EXPERIMENT 3: KINETIC STUDY ON THE FIRST-ORDER REACTION ..................... 12
EXPERIMENT 4: VISCOSITY OF POLYMER SOLUTION ............................................... 17
EXPERIMENT 5: ADSORPTION .......................................................................................... 22
EXPERIMENT 6: SYNTHESIS OF COLLOID SYSTEM AND INVESTIGATION OF THE
COAGULATION .................................................................................................................. 28

1
 EXPERIMENT 1: SATURATED VAPOUR PRESSURE

I. Aim of experiment
To measure the saturated vapour pressure P of a volatile liquid at different temperatures,
derive the Clausius-Clapeyron equation.
To determine the enthanpy of vaporization and the normal boiling temperature of the
liquid.
II. Background
II.1. Saturated vapour pressure
If a volatile liquid is placed in a closed vessel, two processes occur simultaneously:
evaporation (or vaporization) and condensation. In the beginning, the evaporation rate is higher
than the condensation rate. Over time, the evaporation rate does not change. However, the
condensation rate gradually increases. The point at which both processes’ speeds are equal is
called liquid-vapour equilibrium. The vapour pressure of vapour phase at this time is called
saturated vapour pressure.

Figure 1.1. Evaporation and condensation.

At the equilibrium state, the number of liquid molecules that evaporated equals the
number of vapour molecules that condensed. Therefore, the vapour pressure, P, reaches the
maximum value at this time. Then, the vapour pressure P has a constant value over time (if T =
const), and it is called the saturated vapour pressure, often referred to as the vapour pressure.
II.2. Clapeyron-Clausius equation
The vapour pressure depends on temperature according to the Clapayron-Clausius
equation as follows.
d ln P l
= (1)
dT RT 2
Where: P – Saturated vapor pressure
T – Temperature (K)
l - Heat of evaporation
R – Ideal gass constant

2
 In a narrow temperature range, we can consider λ = const, and then transform (1) and take
the unidentified integral, we have:
l A
ln P = - + const = - + B (2)
RT T
From the above equation, we can consider lnP as a linear function of 1/T. Therefore, we
can measure P in different narrow temperature ranges and plots lnP = f(1/T) and derive to find
λ and B as follows:

lnP

M
yM

yN
N

xM xN 1/T

Figure 1.2. Graph of lnP = f(1/T)

- A = tana, with A = l/R
and: l = A. R = - R.tana
Where: tanα is determined from the coordinates of two points (M, N) in the graph lnP =
f(1/T) in Figure 1.2:
∆' '! − '"
!"#$ = =
∆( (! − ("
The value of λ and the value of lnP are obtained from the above graph, replacing these
values in (2) to determine B.
The boiling temperature of a liquid is the temperature at which its vapour pressure is equal
to atmospheric pressure. If P is 760 mmHg, from (2) Ts will be determined as follow:
A
ln760 = 6,6333 = − +B
TS
Note: If the measurement unit of P is converted from mmHg to N/m2 (1mmHg = 133,332
2
N/m ), we have:
A
lnP (N/m 2 ) = − + B'
T
B’ = B + ln133.332 = B + 4.8928
There are many methods to measure vapour pressure. Here, we use the method proposed
by Smith and Menzies, the diagram for the method principle is shown in figure 3. According to

3
the figure: if tube A does not contain air inside and the liquid levels in branch B1 and B2 of the
U-shaped tube are equal:
=> Vapour pressure P = Pressure at B1 = Pressure at B2 = Pressure at M
Because the pressure at M = pressure at L – pressure of mercury column (h)
=>P = H – h (mmHg) (H is atmospheric pressure, mmHg)

Figure 1.3. Diagram for measurement of saturated vapour pressure by Smith and Menzies
III. Experimental
Add the liquid (e.g., acetone, CS2, etc.) into branches A and B and the peach jar (about
2/3 volume) and then connect it to the N-tube. Place this jar into the water. It has to be
submerged in water, as shown in Figure 1.3.
1. Remove air from A in the following way:
Set a temperature (t) in the water bath, turn on the vacuum pump, and then slowly open
the valve J. When the pressure gradually decreases, the liquid level at B2 and M increase, and
the liquid level at B1 and L decrease. The gas bubbles inside A escape out, accompanied by air.
2. Make sure the air in A is removed completely, then lock the valve J. Then, open valve K
slowly to allow the air to come in until the liquid level at B1 equal to the liquid level at B2.
Immediately lock the valve K. At this time, you can write the temperature t, atmospheric
pressure H, and the pressure difference by mmHg level, h.
Attention: Carefully adjust valve K so that air bubbles from B will not enter into A
3. Increase the water bath temperature (about 1 – 1,5oC each time) and move valve K until
the liquid level at B1 equal to that at B2, then measure pressure P at the corresponding
temperature. Determine about 6 – 8 values of pressure P at 6-8 values of temperatures.
4. Make a table of results and draw a graph of lnP = f (1/T) on the drawing paper and
determine λ, B, Ts and establish the Clapeyron-Clausius equation.

Attention:
Please check the tightness of valves and joints before doing experimental.
Do not let the pump work too strong. Let the air bubbles escaped slowly and avoid moving
acetone to C.

4
 Lock or open valves J and K slowly to avoid mercury out the manometer.
Verify the air above A expelled completely by doing a test as follow: at a given temperature,
after measuring h for the first time, keep the temperature constant and remove the air for a
period of time, then measure h again. If two values of h are the same, we can conclude that the
air inside A has been removed completely.
Select two points M and N, located far away from each other to draw the graph with the
highest accuracy.
If λ = [J/mol] please use R= 8.314 J.mol-1. K-1
IV. Questions
1. Why have to remove air completely from A? Why do you have to do as instructed if you
want to know the air above A is removed completely?
2. Why, after removing air from A, we have to adjust valve K to make two liquid levels
B1 and B2, equal? If the B1 and B2 levels are slightly different, how it affects the result? Why?
3. Why is it impossible to determine tgα by protractor the ratio of the length of sides? Is
there any case to do so?
4. How does λ depend on temperature? When the temperature rises, how does λ change?
(Given that the experimental data of heat capacity of a vapour state is usually about 2/3 of it in
a liquid state)

5
 EXPERIMENT 2: DISTRIBUTION LAW
I. Aim of experiment
To determine the distribution constant KD of iodine (I2) in two immiscible solvents that
are carbon tetrachloride (CCl4) and water (H2O).
To determine the equilibrium constant KC of chemical reaction KI + I2 ⇌ KI3 in the
aqueous phase.
II. Background
II.1. The Nernst distribution law
The Nernst distribution law shows the distribution of component X in two solvents A
and B (these liquids are immiscible or miscible to a limited extent). This law is applied to dilute
solutions. The Nernst distribution law states that the concentration ratio of a solute in two
solvents at liquid-liquid equilibrium is constant at constant temperature provided that the solute
is not dissociated/associated in both solvents. The constant is known as distribution constant or
distribution coefficient, and it is expressed as follows:
Concentration of X in A C#/%
= =KD (1a)
Concentration of X in B C#/&
For example, CCl4 and H2O are immiscible. If I2 solute is dissolved in both solvents
(shown in Figure 2.1), from Nernst distribution law, we have:
Concentration of I' in CCl( C)! /*! +
= =KD (1b)
Concentration of I' in H' O C)! /*! +

I2 in water water phase

I2 in CCl4 CCl4 phase

Figure 2.1. Distribution of I2 into CCl4 and H2O solvents.

Since I2 dissolves in CCl4 better than in H2O, the value of distribution constant KD is
quite high. If concentrations of I2 in these two layers are determined, it will lead to calculate
KD .

II.2. Equilibrium constant KC of a chemical reaction

Given a chemical reaction at equilibrium state:
KI + I 2 ⇌ KI3
The equilibrium constant of this reaction is expressed as follows:
[./" ]#$
A, = [/ (2)
! ]#$ .[./]#$

where all the concentrations are determined at the equilibrium state.

7
 There are several methods to determine KC using different methods directly or indirectly.
In this experiment, we use the direct method to determine the concentrations of each chemical
substances by using titration method and distribution law as described below:
When I2 dissolves in "CCl4 – KI solution", we have:
- In the water phase, I2 reacts with KI to form KI3 complex. This chemical reaction has the
equilibrium state KI + I 2 ⇌ KI3.

KI + I! ⇌ KI" water phase

I2 in CCl4 CCl4 phase

Figure 2.2. Distribution of I2 between CCl4 and KI solution.

- In the CCl4 phase, Iodine existed as an I2 molecular state. Thus, I2 takes part into two
equilibriums: chemical equilibrium in the water phase and distribution equilibrium in the water
phase/CCl4 phase. The concentration ratio of I2 in these two phases is distribution constant, KD.
In this experiment, we use the titration method to determine the I2 concentration in two
phases with 1 wt% starch solution as an indicator. The endpoint of the titration is the point at
which the deep blue color of the titrate mixture disappears.
When titration of I2 in KI solution using Na2S2O3, it is impossible to determine I2 alone. It
is because when I2 interact with Na2S2O3 as the following equation:
2Na2S2O3 + I2 = Na2S4O6 + 2NaI
consequently, the equilibrium KI + I2 ⇌ KI3 will move backward to produce I2. Overall, the
total concentration of I2 will be determined as shown below:
[I2]total = [I2]eq + [KI3]eq (3)
The titration of I2 in the CCl4 phase will get [I' ]223% . After determined KD (from equation
(1)), we get:
[/! ]&&'%
[D' ]45 = (4)
.(

From [I2]total and [I2]eq, [KI3]eq will be determined by equation (3). Then, [KI]eq can be
calculated from equation (5) as follows:
[KI ]eq = [KI ]initial - [KI3 ]eq (5)
III. Experimental
1. Prepare bottle (1) and (2) with the compositions as shown below:

Bottle 1 2

Distilled water (mL) 120 -

Solution KI 0.01N (mL) - 50

Solution I2 in CCl4 (mL) 10 10

8
 2. Shake the mixtures vigorously for 15 – 20 mins until distribution equilibrium is
reached.
3. Transfer them to the separating funnel (1) and (2), respectively. Wait until these two
phases are completely separated, then take the I2/CCl4 solution into the dried closed
bottle numbered (1) and (2).
4. Titrate 2 mL I2 in CCl4 with Na2S2O3 0.01 N.
5. Titrate 25 mL I2 in water (from the separating funnel 1) with Na2S2O3 0.001 N
6. Titrate 5 mL solution I2 and KI (from funnel 2) with Na2S2O3 0.001 N.
Each solution must be titrated at least twice or more, and the final result was averaged.
Attentions:
1. Pippet 2 mL used to take I2 in CCl4 must be dry (if it is wet, dry it with acetone before
using).
2. CCl4 is a volatile liquid. It could dissolve a lot of I2 and can not dissolve in Na2S2O3.
Therefore, before taking out 2 mL of I2/CCl4, 5 ÷ 10mL of KI 5% solution should be added into
the beaker in advance. KI will withdraw I2 from the CCl4 phase into an aqueous solution to
perform the titration efficiently and precisely. Besides, KI solution will suppress the
evaporation of CCl4 and prevent the loss of I2 in the CCl4 phase.
3. When taking I2 from the water phase or the KI solution, have to make sure no trace of
I2 in CCl4 remains.
4. Should add starch solution when the amount of I2 is rather small (as shown by the light
yellow color of water phase or light pink of CCl4 drops). Please note that the mixture should be
shaken well during titration of I2 in the CCl4 phase.
IV. Calculation
The reaction of I2 with Na2S2O3 is a redox reaction. In the reaction, 1 mol of I2 exchanges
two electrons. Thus, the equivalent of I2 (E/! ) and molarily of C I = [I 2 ] has expressed as below:
2

1
C I = [I 2 ] = N
2
2 I2
IV.1. Determination of KD
Let V1 is the volume (mL) of Na2S2O3 0.01 N used to titrate 2 mL solution of I2 in CCl4;
V2 is the volume (mL) of Na2S2O3 0.001 N used to titrate 25 mL solution of I2 in H2O
(funnel 1). We have:
0.01H6 = 2(E/! ),,7% = 4[D' ],,7%
0.001H' = 25(E/! )8! 9 = 50[D' ]8! 9
[/! ]&&'% ;
Then: A: = [/! ])! *
= 125 ;+
!

IV.2. Determination of KC
Let V’1 is volume (mL) of Na2S2O3 0.01N to titrate 2 mL solution I2 in CCl4;
V’2 is volume (mL) of Na2S2 O3 0.001N to titrate 5 mL solution I2 in KI (funnel 2).
0.01H′6 = 2(E/! ),,7% = 4[D' ],,7%
<.<6;=+
® [D' ],,7% =
(

9
 0.001H′' = 5(E/! )>?>@7 = 10[D' ]>?>@7
<.<<6;=!
® [D' ]>?>@7 =
6<
<.<6;=+
From equation (4) we have: [D' ]45 = (..,-

From [I2]total và [I2]eq we determined [KI3]eq and [KI]eq from equation (3) and equation
(5), respectively. Then determine KC from equation (2).

V. Questions
1. For the determination of KC, why we have to use CCl4? Can we replace CCl4 with the other
liquid? What are the required properties of the liquid for this experiment?
2. When we take out I2 in the CCl4 phase, if the action is not fast and the beaker is not close,
what will happen?
3. Please compare the color of I2 in water, I2 in KI solution, and I2 in CCl4. Explain why?
4. Please explain why we have to dry the pipette with acetone when taking I2 in CCl4? Could
we use another solvent instead of acetone? If we take I2 in CCl4 by wet pipet, what happens and
how it affects the deviation for the determination? Why don’t we need to dry the pipet to take
I2 in KI solution?

10
 EXPERIMENT 3: KINETIC STUDY ON THE FIRST-ORDER REACTION
I. Aim of experiment
To study the kinetic reaction of the ethyl acetate-catalyzed hydrolysis in the presence of
acid via determining the rate constant, k, and the activation energy E.
II. Background
The hydrolysis of ethyl acetate in the HCl solution is one of the most well-known
reactions in chemistry. It is represented as a model example of the second-order reaction in the
literature dealing with chemical kinetics. The chemical reaction is shown in equation:
CH3COOC2H5 + H2O = C2H5OH + CH3COOH (*)
The rate law of reaction is the second-order reaction:
v = k2 .C H 2O .Ceste (1)

where k2 is the rate constant (or rate coefficient); and CH2O, Cester are concentrations of
water and ethyl acetate in the reaction solution at a given time, respectively.
When the reaction condition is controlled so as to CH 2O >> Cester, the CH 2O are assumed
to be a constant during reaction process, and set k2. CH 2O = k1, then we have:

v = k1.Cester (2)
Therefore, if the water concentration is very high (meaning that the reaction is carried
out in a dilute solution), the reaction (*) will be the pseudo first-order reaction.
So that, the equation of the reaction rate is:
dCeste
v=− = k1 .Ceste
dτ
1 Co
Deduction: k1 = .ln (3)
τ Co − xτ
where: C0 is the ester concentration at the initial of reaction (t = 0);
xt is the ester concentration at the any time of reaction process, t
The rate constant k depends on the temperature following the Arrhénius equation:
d ln k E E
= 2
⇒ d ln k = dT
dT RT RT 2
Integrating with the temperature from T1 to T2, we have:
R.(ln kT2 − ln kT1 )
E= (4)
1 1
−
T1 T2
Where: E is the activation energy
kT1, kT2 are the rate constants at T1 and T2.
Therefore, if we want to calculate the activation energy E, we must determine the rate
constant k at two temperatures T1 and T2.

12
 As shown in equation (3), if we want to determine the rate constant k, we have to
determine the ester concentration with the reaction time. However, the determination of the
ester concentration is difficult so that we can measure the generated acid (acetic acid) at the
period of time. The generated acid can be measured by conductivity method or titration method
(using NaOH). In this experiment, the titration method is chosen.
In equation (3), the initial concentration (C0) of the ester has to be replaced by the
generated concentration of acetic acid (Ca,∞) when the reaction is considered to finish (the
steady-state of the reaction), at the time tending toward infinity, t∞ ; the concentration (xt) of
the ester at any time has to replace by the concentration of the generated acetic acid (Ca,t) at the
time of t. So, we can re-write the equation (3) as follows:
1 Ca,∞
k1 = .ln (5)
τ Ca,∞ − Ca,τ
The procedure to determine the Ca,∞ and Ca,t as following:
At the initial time of the reaction, t0:
V0 (mL) is the volume of NaOH (concentration N) to titrate the volume (V, mL) of the
reaction solution at the initial time. The initial concentration of the generated acid (CH3COOH)
at t0 is the concentration of HCl (as the role of the catalyst) because CH3COOH was not
generated at that time. According to the equivalence law, we have:
V.Ccat = V0.N
N
Þ Ccat = × Vo (6)
V
At the reaction time, t:
Vt (mL) is the volume of NaOH (concentration N) to titrate the volume (V, mL) of the
reaction solution at the time of t. The Vt is the volume of NaOH solution for titrating both the
volumes of the generated acid (CH3COOH, Ca,t) at t and HCl (Ccat). According to the
equivalence law we have:
V.(Ccat + Ca,t) = N.Vt
N
Þ Ccat + Ca,τ = .V (7)
V τ
From equation (6) and (7):
N
Ca,τ = (Vτ − V0 ) (8)
V
If the reaction is assumed to be finished, when t ® ¥, from equation (8), we have:
N
Ca,∞ = (V∞ − V0 ) (9)
V
Replace eq. (8) and eq. (9) to eq. (5) we have:
1 V −V
k = .ln ∞ 0 (10)
τ V∞ − Vτ

13
 The rate constant, k, of the hydrolysis of ethyl acetate in the HCl acid is calculated by
equation (10).

III. Experiment
III.1. Determining V∞
Because the reaction is slow, the hydrolysis of ethyl acetate must be carried out at a
temperature between 70 - 80oC for 2.5 hours to determine V∞.
Firstly, preparing a round bottom flask (100 mL) reactor containing 50.0 mL of HCl 0.1
N (catalyst), and then 2.0 mL of ethyl acetate is quickly added to the reactor to account for the
start of the reaction. Secondly, the reflux condenser is inserted into the round bottom flask and
placed this system in a water bath (Figure 3.1). The temperature of the water bath is set in the
range of 70 - 80oC. The reaction is carried out in at least 2.5 hours.

Reflux condenser

Therometer

Water bath

Reaction solution

Figure 3.1. Schematic diagram of the experimental setup for determining V¥.
After 2.5 hours, the reaction solution is taken with 5.0 mL by pipet and put into a flask
(100 mL) to be titrated CH3COOH and HCl by NaOH (0.05 N) with phenolphthalein as an
indicator. After that, this reaction will be carried out continually in the water bath at a
temperature from 70 - 80oC for 10 minutes. Then, the volume of the reaction solution (5.0 mL)
is titrated again. If the volume of NaOH used in this titration step is differs from the first time,
it is said that the reaction was not finished (reached the steady-state). The reaction has to be
carried out until the volume of NaOH from twice titrated is constantly (with £ 0,1 mL of the
deviation). Then, the reaction is considered finishing, and volume V∞ is recorded.
III.2. Determining the activation energy E
To calculate the activation energy (E) of the reaction (following eq. (4)), the two value
of kT1 and kT2 (at two temperature T1 and T2) has to determine.

1. Determining kT1 and kT2

We take place the experiments for determining kT1 and kT2 in parallel with the
experiment of determining V∞. The two experiments of determining kT1 and kT2 are similar in

14
terms of steps. In this part, we present the instructions on how to carry out the experiment of
determining the kT2 only.

Determining kT2
The kT2 is the rate constant at temperature T2 (this temperature will higher 10oC than
room temperature, it means T2 = T1 + 10 (K)).
- Take 50 mL of HCl 0.1N (as a catalyst) into an Erlenmeyer conical flask with a cap
(100 mL). This flask is numbered (2).
- Place the conical flask in a water bath at a temperature 10oC higher than room
temperature for 5 ÷ 10 minutes to stabilize the temperature. Then, 2 mL of acetate acetyl is
added to the conical flask is numbered 2 by using a dry pipette (2 mL).
Note: When half of the volume of acetate acetyl is added to the conical flask, record this
time as the initial time of the reaction (τ0).
Shake the conical flask gently and immediately withdraw 5 mL (by a 5 mL pipette) of
the reaction solution into another Erlenmeyer flask containing 20 mL of cold distilled water (~
5oC) and phenolphthalein as an indicator. The use of cold distilled water is for slowing down
the reaction rate. Then, titrate it with NaOH (0.05 N). This volume of NaOH is recorded as V0.
After every 20 minutes (20, 40, 60 minutes), 5 mL of reaction solution are titrated by
NaOH.
Record these volumes of NaOH as Vt into the table in the experiment report.

Determining kT1
The reaction of this experiment is taken alternately with the experiment for determining
kT2 but it is taken at room temperature with the same steps as the experiment for determining
kT2 . The Erlenmeyer Conical Flask for this reaction is numbered (1). These volumes of NaOH
used to titrate, Vt, are recorded in the experiment report.
V¥ is used to calculate kT1 and kT2

IV. Question
1. Why the experiment for determining V∞ must be carried out at 70-80oC? What will it be at
room temperature? Why is a reflux condenser used during this experiment, as shown in
Figure 1?
2. Explain the steps to determining the V∞. In principle, are the two values of V∞ determined
from two consecutive times of titration similar? Why?
3. Explain why 20 mL of cold distilled water is used to slowdown the reaction rate in the
titration step.
4. Describe the method for determining the rate constant k by using the graphic method?
5. Write the units of the reaction rate (n), the rate constant (k) of the first-order reaction, and
the activation energy (E)
6. In this experiment, what steps will get the errors?

15
 EXPERIMENT 4: VISCOSITY OF POLYMER SOLUTION

I. Aim of experiment
To determine viscosity and specific viscosity of a polymer solution polyethylene glycol
in water.
II. Background
When an external force (F) is applied on a thin layer which is parallel to the surface of
the liquid, the layer will move with the relatively slow velocity u1.
Simultaneously, the next layers will also move; their velocity is slower than u1 (Figure 4.1).
The direction of the external force and internal friction force are opposite. In constrast, their
values are same and proportional to the cross-section S and proportional to the speed gradient
between layer du/dx layers. The relationship is expressed in formula (1):
du
F = η.S. (1)
dx
where h is the viscosity coefficient or viscosity (dynamic viscosity). The unit of h is Poise (P)
(1 P = 0.1 N.s/m2).
u1

1
x

u2
2

Figure 4.1. The velocity of sequent layers.

In measurement, viscosity can be determined either by moving a solid body through the
liquid or by allowing the liquid itself to flow through a capillary. In practice, several kinds of
viscosity are used.
+ Relative viscosity hrel:
M
MA47 = (2)
M?
where h is the viscosity of the solution, ho is the viscosity of the solvent.
+ Specific viscosity hs:
M − M? M
MB = = − 1 (3)
M? M?
+ Reduced viscosity:
MB
MA4C = (4)
O
where C is the concentration of the solution.
The viscosity measurement of a polymer solution plays an important role in determining
the molecular weight, structure, and various properties of the polymer. The viscosity of a
polymer solution is generally much higher than that of a normal solution or a colloid system

17
with the same concentration. Therefore, it is required that the polymer solution used in viscosity
measurement has a very dilute concentration.
Staudinger and co-workers found that the reduced viscosity of polymer solution hr/C
increase with the increment of its concentration. In the range of low concentration, the reduced
viscosity is proportional to the concentration of the polymer solution. (Figure 4.2).
η/C
2

1
[η]

Figure 4.2. The dependence of reduced viscosity on concentration of a solution. 1. Normal

solution; 2. Polymer solution.
Intrinsic viscosity is defined as follows:
MB
[M] = lim (5)
,⟶< O

Therefore, the relationship between specific viscosity and concentration is as follow :

hs/C = [h] + aC (6)
III. Experimental
III.1. Chemical and equipment
Chemical:
- Distilled water
- Polyethylene glycol (PEG) solutions with concentrations: 5; 8; 10; 15; 20; and 25 w/w%
Equipment
- 01 Ostwald viscometer Φ 0.8 mm 1 2
- 01 stop watch
- 01 two-litered beaker
- 01 thermometer a
- 02 pipet 10 mL b
- 01 pipetting ball
- 01 stand
III.2. Guidance of experiment procedure
Use Ostwald viscometer
In this experiment, we use the Ostwald Figure 4.3: Ostwald viscometer
viscometer to measure dynamic viscosity. The viscometer is a U-shaped tube that includes a
capillary (Figure 4.3). In the capillary (numbered 2) is marked two points a and b.

18
 Before the measurement, the viscometer is washed, then rinsed with distilled water. The
viscometer is put in a water bath to keeping the temperature constant. The water level in the
water bath should be higher than point a in the capillary.
Use a pipet to take 10 mL of a liquid, then pour in the capillary numbered 1. Use a
pipetting ball to push the liquid to be 1 cm higher than point a. Let the liquid naturally flow
from the point a to b. Write down the flow time of the liquid when it runs from point a to b.
Repeat the procedure at least 3 times to get the average value.

Measure the viscosity of aqueous polyethylene glycol

Set temperature at 20o or 25oC, measure the flow time from the point a to b of distilled
water, aqueous polyethylene glycol solutions with concentrations: 5; 8; 10; 15; 20; and 25
w/w%.
Note: wait at least 5 minutes until the temperature in a water bath is constant, then measure the
flow time.

Calculate the viscosity

When a liquid runs in a capillary, its viscosity is proportional to its flow time t and
density r. The relationship is as follow
h = k.r.t (P) (7)
where k is viscometer constant.
We can determine k by measuring the flow time of distilled water of which viscosity is
known.
ho = k.ro.to (P) (8)
ho is the viscosity of distilled water (see Table 1 in this experiment), ro is the density of
distilled water, to is the flow time from the point a to b of distilled water.
Divide (6) to (7):
h r ×t
= (9)
ho r o × t o
ρ.t
Therefore: η = η0 (10)
ρ0 .t 0
When polymer solution is dilute, it is assumed that r = ro, so
t
η = η0 (11)
t0
The specific viscosity is calculated according to equation (3). When we replace h in
equation (10) into equation (3), specific viscosity is calculated according to the equation:
!
MB = − 1 (12)
!?

19
 As shown in equation (5), the value of intrinsic viscosity [h] can be calculated by
extrapolating the graph of reduced viscosity to zero concentration.

Table 1.1. The viscosity of water at different temperature.

Temperature,
0 10 20 25 30 40 50 60
(oC)

ho (mN.s/m2) 1.792 1.308 1.005 0.894 0.801 0.656 0.549 0.469

IV. Questions
1. Why does temperature have to keep constant during the measurement of viscosity?
2. Why should a polymer solution run slowly during measurement of viscosity using Ostwald
viscometer? Explain.
3. How does the viscosity of a liquid depend on temperature? Explain.

20
 EXPERIMENT 5: ADSORPTION
I. Aim of experiment
- To use the method of surface tension measurement to study the adsorption in the solution.
- To determining ao and K constant in Langmuir’s equation for activated carbon adsorbing
butanol C4H9OH from the solution.
II. Background
II.1. Relationship between surface tension and concentration of a solution
When a surfactant was dissolved into water, the surfactant molecules will be adsorbed
on the liquid – gas interface. This adsorption causes the reduction of the surface tension of
solutions.
The surface tension σ of the surfactant solution decreases with the increase of the
concentration of surfactant molecules in the system. Therefore, if the solution is reduced
somehow, the adsorption of surfactant on the liquid-gas interface decreases and the surface
tension increases.
At a given temperature, the surface tension of the solution depends on the concentration
of surfactants according to the experimental Szyszkowski Equation:
s = so – a.ln (1 + b.C) (1)
where: s, s0 are the surface tension of butanol solution (C mol/L) and distilled water,
respectively,
a, b are experimental constants (depending on the solvent, substance).
Based on the Szyszkowski equation, we can build the graph that shows the relationship
of the surface tension (σ) and the concentration of butanol (C) (the calibration curve).
Conversely, if the surface tension of the solution is determined (σ’), the solution concentration
can be calculated (C’) by interpolating method, as shown in Figure 5.1.
In this experiment, we measure the surface tension of the aqueous solution of C4H9OH
at different concentrations (detailed in the experiment section). The surface tension (σ) depends
on the concentration of surfactants (C) in the isotherm condition, and this dependence is shown
in Figure 5.1.
σ

σ0

σ’
σ1

0 C’ C1 C

Figure 5.1. Schematic representation of typical surface tension isotherm of water/surfactant

solution, calibration curve s - C.

22
 Theoretically, when an adsorbent (e.g., activated carbon) adsorbs an adsorbate (e.g.,
Butanol) in solution, the concentration of the solution will be decreased. After the adsorption
process, the butanol solution is separated from the mixture of Butanol – Activated carbon by
filtering, and then this butanol solution is measured the surface tension. Based on this measured
value of surface tension, the concentration of butanol solution (C’) (after adsorption processing)
can be determined by interpolating from calibration curve s - C (Figure 1). The adsorbability a
is calculated by the equation:
Co − Caf
a= ×V (mol/gr)
m
Where: Co, Caf (mol/L): concentration of butanol solution before and after adsorption
process; V (Litter): total volume of solution (in adsorption process); m (gr): mass of adsorbent.
Note: the Caf is the concentration of the solution at the equilibrium adsorption.
II.2. The adsorption isotherm: Langmuir adsorption equation
- The adsorption isotherm in solution is assumed as the Langmuir adsorption model, and the
Langmuir adsorption equation is the following:
K.C
a = ao × (mol/gr)
1+ K.C
Where: a (mol/g): adsorbability at the equilibrium adsorption (Caf)
ao (mol/gr): the maximum adsorbability
K (L/mol): constant for each adsorbent – adsorbate pair at a given temperature.
The ao and K are constants of Langmuir’s equation. Generally, to estimate the ability of
each adsorbent, the a0 and K need to be determined. These values are calculated using the
graphic method based on the relationship: C/a = f(C). This graph is built by experimental data,
shown in Figure 5.2.

C
a

α
A

O
0 C

Figure 5.2. Schematic representation of the relationship of C/a = f(C), and the determination
method of ao, K.
The ao and K values are equal:
1
!"#$ =
"?

23
 1
and OA =
K.ao
III. Experiment
III.1. Chemicals and equipment
- The equipment system of the surface tension measurement is based on the Maximum bulk
pressure method, Figure 5.3.

2 3
1
5

9 6
4

7
8

Figure 5.3. Schematic representation of the system of the surface tension measurement based
on Maximum bulk pressure method. (1) Sample container; (2) Capillary tube; (3) T junction;
(4) Water bath for stabilizing temperature; (5) Thermometer; (6) Pressure reducer; (7)
“Stopcock” for adjusting the pressure reduction; (8) Beaker (liquid reservoir); (9)
Manometer;
- 4 Erlenmeyer conical flasks with cap (100 mL) were numbered 1 to 4 (for carrying out
the adsorption process)
- 4 Erlenmeyer conical flasks with cap (100 mL) were numbered 1’ to 4’ (for containing
separated solution by filtering after the adsorption process)
- Burette (25 mL)
- Activated carbon (powder 200 – 300 mesh)
- Butanol solution with different concentration: 0.1; 0.2; 0.3 and 0.4 M
Note: All the glassware needs to be cleaned and dried
III.2. Measurement method of the surface tension:
The equipment system for this experiment is shown in Figure 3. The principle of this
method is based on the differential pressure between inside the sample container and outside.
This differential pressure is measured thanks to a manometer (9). The surface tension (s)
concerns with the differential pressure (h) as follow:
h = K’. s
Where: K’ is the constant, depending on only temperature and equipment system, it
means that h corresponds to s. Basically, we have to build the calibration curve “s - C” in this
experiment (Figure 1); however, we can build the calibration curve “h – C” thanks to the

24
correspondence of h and s (Figure 4). Therefore, we have to measure h value (by manometer),
but we do not need to measure the surface tension.
After the adsorption process, we can calculate the adsorbability (a) by determining the
concentration of butanol solution before (Co) and after (Caf) the adsorption thanks to the
calibration curve, Figure 5.4.
h

h0

h’
h1

0 C’ C1 C

Figure 5.4. Schematic representation of the calibration curve s - C; h – C.

The principle of the surface tension meter (Figure 5.3):
- Pour the sample into the sample container (1) with suitable volume.
- Plug the capillary tube (2) in sample container; Note: Let the tip of the capillary touch the
liquid surface (1).
- Place the sample container with the capillary tube in a water bath (4) with the thermometer
(5). Note: the temperature has to be kept constant during the surface tension measurement
process.
- Check the vacuum-tightness of the system before measuring the first liquid.
- Steps of the experiment: open the stop-cock (7) slowly to let water in the pressure reducer
(6) flows out to the beaker (8). We need to control the stop-cock (7) slowly to a bubble that
goes out of the capillary tip (2) in about 10 seconds. When there is a bubble going out of the
capillary, the value of h will be maximum. We have to record this value and repeat this step
when there is another bubble going out of the capillary tip.
III.3. Experiment of adsorption
- Weigh 1 gram of activated carbon and put it into a flask (No. 1), and repeat for other flasks
(No. 2, 3, and 4).
- Then add precisely 25 mL (using burette) Butanol solution with concentration 0.1; 0.2; 0.3
and 0.4 M into 4 flasks (contained 1 gam of activated carbon) correlatively.
- Set these 4 flasks to the orbital shakers and take the adsorption process in 60 minutes.
- Measure ho (distillated/DI water) and hi (i = 1 ® 4, corresponding to initial concentration of
butanol solution, C1 = 0.1 M; C2 = 0.2 M; C3 = 0.3 M; C4 = 0.4 M).
- After 60 minutes of the adsorption process, the adsorption process was achieved equilibrium.
The mixture of butanol solution – activated carbon is separated by filter paper. Then, the
filtered liquid (filtrate) is measured by the surface tension by measuring the differential
pressure. These values of the differential pressures are named hi’ (i = 1 ® 4, corresponding
to the concentration of butanol solution, from C1’ to C4’, after the adsorption process.
- The concentration of the butanol solution after the adsorption process will be determined
from the calibration curve (Figure 5.4).
Note:
25
 ü The water level in the pressure reducer (6) needs to be kept changing as little as possible.
ü When measuring hi or hi’, the solution with lower concentration is measured first and
then turning into the solution with more condensed concentration.
ü The ho, h, and h’ need be recorded carefully on the manometer and the calibration curve
“h – C”.
ü Keep the rate of reducing pressure in the pressure reducer unit (6) as same as possible
for all the measures of ho, h and h’.
ü Rinse the glassware carefully in each measurement.
IV. Question:
1. Why we have to keep temperature stable during the experiment?
2. Why the surface tension change when activated carbon is added to the butanol solution?
3. The manometer (9) can be tilted to the vertical in the measurement of ho, hi, and hi’. Explain
this ideal?

26
 EXPERIMENT 6: SYNTHESIS OF COLLOID SYSTEM AND
INVESTIGATION OF THE COAGULATION
I. Aim of experiment
- To prepare the ferric hydroxide sol
- To determine the coagulation value of the sol in the presence of certain electrolytes.
II. Background
Colloidal system or dispersion system is a heterogeneous system which is made up of a
substance (dispersed insoluble particles) with the size of about 10-9 - 10-7 m and distributed into
the volume of another substance (called the dispersion medium).
Colloidal systems are micro-heterogeneous systems with a large interfacial surface, so
they are thermodynamically unstable.
Requirement of synthesizing a stable colloidal system (two basic conditions):
1. Dispersed substances are insoluble or less soluble in the dispersion medium
2. In the colloidal system, it is essential to have substances playing as protectors to block
the micelles aggregation due to the sum of the interaction forces between particles. Those
substances could be added into the studied system or formed during the synthesis of the colloid.
There are two principal ways to prepare colloids: Dispersion of large particles or droplets
to the colloidal dimensions and condensation of small molecules into larger colloidal particles.
This experiment employs the reaction of the hydrolysis of ferric chloride with boiling distilled
water as per the reaction:
FeCl3 + 3H2O ⇌ Fe(OH)3 + 3HCl
The above reaction is the reversible reaction. At the high temperature, the reaction moves
to the forward direction of the reaction. Since the solution now contains excessive HCl, the acid
should be removed by dialysis.
Ferric hydroxide sol is the positive colloid, with the color of wine red.
When there is a protective agent in the system, the colloid system is metastable. When the
metastable state is hindered, particles aggregate in clusters, and they are removed from the
dispersion medium in the form of a large cluster via aggregation and sedimentation phenomena.
It is the coagulation.
The coagulation could happen under certain conditions: adding electrolytes into the
system, mixing, heating, or cooling the system, etc.
To estimate the electrolyte’s ability to make coagulation, the concept of coagulation value,
g, is employed. The coagulation value is defined as the minimum concentration of the studied
electrolyte that makes the coagulation observable. The unit of the coagulation value is mol.L-1
or eq.L-1. The coagulation could be observed based on the color change or how the destabilized
particles are further aggregated and enmeshed into larger precipitates, such as turbid or
precipitate state.
III. Experimental
III.1 Chemicals and equipment
Chemicals:
- KCl 4N

28
- FeCl3 (3%)
- Na2SO4 (0.0012N)
- Na2SO4 (0.0018N)
Equipment
- 01 beaker 250 mL
- 01 graduated cylinder 100 mL
- 01 pipette 2 mL
- 05 pipette 5 mL
- 01 pipette holder
- 01 test tube holder
- 01 hot plate
III.2. Experimental procedures
Preparation of ferric hydroxide sol in water
Add 60 mL distill water into the 250 mL beaker, then start the hot plate to boil the liquid.
When the water is boiling, turn off the hot plate and leave the beaker on the hot plate. Use the
pipette to transfer 5 mL FeCl3 3% solution into the boiled water in the beaker. Observe the
phenomenon of forming the ferric hydroxide sol and describe the whole phenomenon in the lab
note or lab report.
Determining the coagulation value of the ferric hydroxide sol
a. Get six test tubes and add substances following with the below table:

Test tube 1 2 3 4 5 6

Distilled water (mL) 3.0 2.5 2.0 1.5 1.0 4

Ferric hydroxide sol (mL) 2 2 2 2 2 2

KCl 4 N solution (mL) 1.0 1.5 2.0 2.5 3.0 0

Observe the coagulation happen and determine the coagulation value

b. Get eight testubes and add subtances following with the below table:

Test tube 1 2 3 4 1' 2' 3' 4'

Distilled water (mL) 2.0 1.5 1.0 0.5 2.4 2.0 1.6 1.2

Ferric hydroxide sol (mL) 2 2 2 2 2 2 2 2

Na2SO4 0.0012 N (mL) 2.0 2.5 3.0 3.5 - - - -

Na2SO4 0.0018 N (mL) - - - - 1.6 2.0 2.4 2.8

Observe the coagulation happen and determine the coagulation value.

Calculating the coagulation value:

The coagulation value, g, is calculated according to the following formula:

29
 C.Vdl
γ= [eq.L-1]
Vtc

Where: C – concentration of the electrolyte [eq.L-1]; Vdl – volume (mL) of the

electrolyte solution; Vtc – total volume (mL) including the sol, electrolyte solution, and distilled
water.
Based on the definitions of fluctuation and observe the reality phenomenal in a lab a
and b to calculate the coagulation value. Note that the two calculated coagulation values should
be matched. In case of a mismatch, students need to check with the reference tattoo test tubes
to clearly observe the coagulation happened.
IV. Questions
1. What are the characteristics of the colloid system?
2. Write the structure of the micelle of the ferric hydroxide sol
3. Explain the role of Na2SO4 and KCl on the coagulation of the ferric hydroxide
4. Which factor does the coagulation threshold depends on? And how does the coagulation
depend upon them?

30
 HANOI UNIVERSITY OF SCIENCE AND TECHNOLOGY
SCHOOL OF CHEMICAL ENGINEERING
DEPARTMENT OF PHYSICAL CHEMISTRY
--------------

Experimental Physical Chemistry

-------------
Reports

Experiments of Physical Chemistry

(CH3082E and CH3007E)
(For the Advanced program in Technology of Pharmaceutical
chemistry)

© Dept. Physical Chemistry, 1/2023

 RESULTS AND DISCUSSION
EXPERIMENT 1
Name:……………………………………………………………………………………
Student ID: ……………………………………………………………………………..

o
Room temperature: t = C ; Atmospheric pressure: P = mmHg

toC

T (K)

1/T

h (mmHg)

P (mmHg) = H - h

lnP

Draw the graph lnP = f(1/T) on the drawing paper, or use a sorfware to draw the graph
Determine the values:
tanα =
λ= (J/mol)
Ts = (K)
Clausius – Clapeyron equation that you determined:

Discussion on the result

Answer the questions:

6
 RESULTS AND DISCUSSION
EXPERIMENT 2
Name:……………………………………………………………………………………
Student ID: ……………………………………………………………………………..

Room temperature: toC =

Determination of KD:
Result of titration:
No 1: V1 (mL) = V2 (mL) =
No 2: V1 (mL) = V2 (mL) =
V1(average) (mL) = V2(average) (mL) =
KD =

Determination of Kc:
Result of titration:
No 1: V’1 (mL) = V’2 (mL) =
No 2: V’1 (mL) = V’2 (mL) =
V’1(average) (mL) = V’2(average) (mL) =
KC =

Discussion on the result

Answer the questions:

11
 RESULTS AND DISCUSSION
EXPERIMENT 3
Name:……………………………………………………………………………………
Student ID: ……………………………………………………………………………..

Room temperature toC = V¥ (mL) =

Flask 1: t1 (oC) = Flask 2: t2 (oC) =

Time, Volume NaOH, kT1 , Time, Volume NaOH, kT2 ,

(minute) (mL) (min-1) (minute) (mL) (min-1)

t=0 V0 = t=0 V0 =

t1 = V1 = k1 = t1 = V1 = k1 =

t2 = V2 = k2 = t2 = V2 = k2 =

t3 = V3 = k3 = t3 = V3 = k3 =

Average value kT1 = Average value kT2 =

Calculating the activation energy E:

Discussion on the result

Answer the questions:

16
 RESULTS AND DISCUSSION
EXPERIMENT 4
Name:……………………………………………………………………………………
Student ID: ……………………………………………………………………………..

Roome temperature (oC):

Viscosity of distilled water at the room temperature: ho = (mN.s/m2)
Flow time of distilled water: to= (second)

Determination of viscosity of the polyethylene glycol solution:

Concentration of
t h
PEG hs hs/C Note
(second) (m.N.s/m2)
(w/w%)
5
8
10
15
20
25

Draw the graph hs/C = f(C) on the drawing paper, or use a sorfware to draw the graph.
Determine the intrinsic viscosity
[h] =

Discussion on the result

Answer the questions:

21
 RESULTS AND DISCUSSION
EXPERIMENT 5
Name: ………………………………………………………………………………………….
Student ID: ……………………………………………………………………………………

Temperature: toC =
Volume of butanol solution: Vb (mL) =

Before the adsorption process

ho (mm) =

Flask 1 Flask 2 Flask 3 Flask 4

C (M) 0.1 0.2 0.3 0.4

h (mm)

After the adsorption process

Flask 1’ Flask 2’ Flask 3’ Flask 4’

h’ (mm)

C’ (M)

C’/a

Plotting the graph: “C'/a = f(C’)”

Determining the absorbability: a0 =
Determining the absorption constant: K=

Discussion on the result

Answer the questions:

27
 RESULTS AND DISCUSSION
EXPERIMENT 6
Name: ……………………………………………………………………………………
Student ID: ……………………………………………………………………………..

Preparation of the colloid system

Observation of the preparation of the ferric hydroxide sol:

Determining the coagulation value

a. In the presence of KCl solution
- Coagulation phenomena (test tube 1; 2; 3; 4; 5; 6)
- Concentration of the electrolyte concentration: C (eq.L-1) =
- Volume of the electrolyte, Vcđl (mL) =
- Total volume Vtc (mL) =
Þ Coagulation value: g=

b. In the presence of Na2SO4 solution

- Coagulation phenomena
Test tube 1; 2; 3; 4 Test tube 1’; 2’; 3’; 4’
Coagulation value g = Coagulation value g’ =

Discussion on the result

Answer the questions:

31