1

CONTENTS

SL.NO LIST OF EXPERIMENTS PAGE

NO.

CYCLE – I

1 HEAT OF SOLUTION BY SOLUBULITY METHOD 2

2 EQUILIBRIUM CONSTANT DETERMINATION 4

3 LIQUID – LIQUID EQUILIBRIUM 7

4 EXCESS PROPERTY DETERMINATION 10

5 VAPOUR COMPRESSION REFREGERATION 13

CYCLE – II

6 COTTRELL BROWN BOILING POINT APPARATUS 16

7 OTHMER VLE STILL 20

8 AIR WATER HEAT PUMP 23

 2

DEMONSTRATION EXPERIMENTS

BOMB CALORIMETER

JUNKER’S GAS CALORIMETER

EXPERIMENT
ONE

HEAT OF SOLUTION BY SOLUBILITY METHOD

AIM:
To determine the solubility of the given solute in the given solvent at different
temperatures ranging from 30 oC to 70 oC and to plot a graph of solubility against the
temperatures ; to calculate the heat of solution, by estimating the amount of solute dissolved at
various temperatures, using titration against KMnO4 or Na2SO4 as the case may be.
THEORY:
Variation of the solubility of a substance with temperature is given by
Vant-Hoff’s Equation

d ( ln ln S) ∆ H0
( dT )( )
=
RT2
 3

S -- Solubility of the substance.

∆ H 0 -- Heat of solution.
R -- Molar gas constant.
T -- Absolute temperature.

Assuming ∆ H 0 is constant over a temperature range T1 to T2, we obtain by integration

S1 ∆ H0
1 1
ln
S2 ( )
( ) (T T )
=
R
−
2 1

S2
ln ( )(
S1
=
−∆ H 0
2.303 R )( TT−TT )
1

1 2
2

PROCEDURE:
Water is taken in 400 ml beaker and gradually heated, upto 700C. K2Cr2O7 crystals are
added slowly with stirring; saturated solution is prepared at 70 0C. The solution is allowed to
cool. A known volume of the liquid is pipetted out at a particular temperature [ say 65 0C ] (the
solution can be drawn off using a pipette packed with glass wool) in a standard flask, diluted if
necessary, and portion of it is acidified with dil H 2SO4. 10 % KI is added and titrated against
saturated solution of Na2S2O3 using starch as indicator. The amount of K 2Cr2O7 dissolved at that
temperature is estimated . The solution in the beaker is allowed to cool further. Another known
volume of K2Cr2O7 solution at different temperature (say 600C) is taken out and the amount is
estimated as above. The titration is repeated with the same volume of K2Cr2O7 solution at
different temperatures say 55oC, 50oC, 45oC,40oC, and 35oC and the amount is estimated.
The experiment can be employed in the case of determination of heat of solution of
benzoic acid, the amount can be estimated with standard NaOH and in the case of Ammonium
oxalate, standard KMnO4 can be used.

MODEL CALCULATIONS:
Determination of solubility at ______ 0C.
By volumetric principles, V1N1 = V2N2
V1 = Volume of dichromate solution
N1 = Normality of dichromate solution.
V2 = Volume of Na2S2O3 solution
N2 = Normality of Na2S2O3 solution
Equivalent weight of dichromate = 49 g/gm equivalent
 4

Solubility at ______ oC = ______ gm/lit.

Similarly, solubility at ____ oC = _______ gm/lit.
Using Vant – Hoff’s equation
R = 8.314 J mol-1 K-1 = Cal mol-1 K-1
∆ H = ________ Cal mol-1

Observation :

Sl.No. Volume of Temp Volume of Solubility

K2Cr2O7 Na2S2O3
o
ml C ml gm lit-1

RESULT:
The heat of solution of the given K2Cr2O7 solution by solubility method was found to be
__________ Cal / mole.

EXPERIMENT
TWO

EQUILIBRIUM CONSTANT DETERMINATION

AIM:
To determine the equilibrium constant for the given reaction at atmospheric pressure and
temperature.
KI + I2 ↔ KI3

I2+ I ↔ I3

THEORY:

According to the distribution law, “A solid or liquid distributes itself between two
immiscible solvents in such a way that the ratio of its concentrations in the both solvents is
constant” provided

1. The temperature remains constant.

 5

2. The substance dissolves in both the solvents in the same form.

3. No chemical combination takes place between the solute and either of the solvents.
4. The concentration of the solute is low.

The ratio of concentration in the two solvents is called the partition co-efficient or
distribution co-efficient. However the distribution law doesn’t hold good in the distribution of
iodine between CCl4 and aqueous KI. This is due to the formation of iodine complex KI 3in the
aqueous KI. But if the concentration of free iodine is taken into the consideration the distribution
law might hold good. The total concentration of iodine in the aqueous layer is given by

Total concentration of iodine = Cl2 = Cl2 (free) + Cl3

This concentration of I2 is determined by titrating with standard Na2S2O3 solution. Similarly,

the concentrations of I2 in organic layer can also be determined by titrating with standard
Na2S2O3.

( Concentration of free iodine∈aqueous layer )= ( Concentration of iodine∈organic layer

partition co−efficient )
Then the value of Cl3 is calculated, provided the initial concentration is known.

Knowing the values of Cl3, Cl2, Cl the equilibrium constant is calculated using the formula.

Cl 3
K=
Cl2 Cl

Let

The concentration of iodine in organic layer = C1 mol lit -1

The concentration of iodine in aqueous layer = C2 mol lit -1P

Partition co-efficient of iodine between organic layer and aqueous layer = Ko { let Ko = 83.18 }
Concentration of free iodine in aqueous layer = C1/Ko mol lit-1

Concentration of KI3 (formed) =

( Total I 2 concentration∈aqueous layer ) −( Free I 2 concentration )
C1
= C2 -( )Ko
mol. lit1
 6

Since one mole of I3 is formed from one mole of the I , the concentration of free KI at
C1
[ ( )]
equilibrium is given as C3- C 2−
Ko
mol. Lit-1

Where
C3 is initial concentration of I.
The equilibrium concentration is given by the relation

C1

K=
[ C 2−
( )]
Ko

C1 C
( ){
Ko [ ( ) ]}
C 3− C 2− 1
Ko

PROCEDURE:
Prepare 250 ml of M/10 KI solution. From this solution, prepare 100 ml of M/15 KI and
100 ml of M/20 KI solutions. Then take 100 ml of M/10 KI solution and 10 ml of saturated I 2 in
CCl4 solution in bottle A.
In bottle B pipette out 100 ml of M/15 KI solution, 7.5 ml of saturated I 2 in CCl4 solution
and 2.5 ml of CCl4 solution.
In bottle C pipette out 100 ml of M/20 KI solution and 5 ml of CCl 4 solution, 5 ml of
saturated I2 in CCl4 solution.
The bottles should be kept in a water bath at ambient temperature and pressure for about
30 min with periodic shaking of bottles.
After 30 min, the organic layer and aqueous layer obtained in each bottle were measured
using a measuring jar.

BOTTLE A:
Entire amount of organic layer is titrated against standard Na2S2O3 solution. Using
standard procedure. Entire amount of aqueous layer is titrated against standard Na2S2O3 solution
using standard procedure. The titration values are noted. The above procedure is repeated for the
other two bottles. Readings were tabulated and equilibrium constants were calculated.

RESULT:
 7

The equilibrium constant for the given reaction at atmospheric temperature and pressure
is found to be _____________ mol. lit-1.

EXPERIMENT
THREE

LIQUID - LIQUID EQUILIBRIUM

AIM:

To draw the solubility curve and tie – lines for the given ternary system.
 8

PRINCIPLE INVOLVED:

All extraction systems are multicomponent and the simplest systems contains a
minimum of three components, a solute , a solvent and diluent. The solute is the material to be
extracted from the feed mixture (solute and diluent) using a solvent which must not be
completely miscible with the diluent.

If the three components are liquids, then the system can be classified into three
types based on the number of partially miscible binaries. Type I system contains only one
partially miscible pair as in the Benzene – Acetic acid – Water system. The system n – Heptane –
Cyclohexane – Aniline containing two partially miscible binaries is type II system. Type III
system containing 3 non – consolute pairs is uncommon, Succinic nitrate – Ether – Water system
is an example.

For all 3 component system, the degree of freedom is the composition of

components. So carry out the experiment at constant temperature and pressure.

Knowledge of equilibrium properties is of great importance in extraction

calculations. It is common practice to use a phase diagram to show the relationship among these
equilibrium properties.

This kind of diagram shows two sets of data.

The solubility curve which shows the boundary between the homogeneous and the
heterogeneous regions of the system. The portion of the diagram under the solubility curve has
two phases (that is heterogeneous). This equilibrium or solubility curve represents the limiting
solubilities.

The equilibrium lines known as tie – lines connect the compositions of the
respective co – existing phases or conjugated solution lying on the bi-nodal curve.

CONJUGATED SOLUTION:

If A and B are two components forming a binary mixture, a solution A in B and a

solution B in A are formed on stirring, then the solution is said to be conjugated solution.

PROCEDURE:
 9

System 1: Nitrobenzene-Acetic acid-Water.

System 2: Benzene-Acetic acid – Water.

Carry out the experiment at room temperature.

1. Prepare various compositions of binary mixtures ( Nitrobenzene-Water) by volume. It

forms two layers.
2. Add third component (Acetic acid) dropwise until two layers disappear and forms
homogeneous solution. Note the burette reading.
3. The miscibility composition is tabulated.
4. Plot the graph by converting the miscibility composition in terms of weight fraction.
5. Draw the solubility curve.
6. From the graph choose a mixture composition, which lies in the heterogeneous region
(portion under solubility curve), and prepare it.
7. Shake it well and allow it to settle. Two layers will be obtained.
8. Remove the extract or raffinate layers and analyze it for any one of the components
(solute or solvent). (Here solvent acetic acid is analyzed).
9. Carry out the same analysis of acetic acid by titrating the extract with sodium carbonate
Na2CO3.
10. Carry out the same analysis for the other layer.
11. The two ends of the tie line composition are obtained from the above two analyses.
12. Draw the tie line.
13. Similarly, draw another tie line by choosing another heterogeneous composition.

Model graph:

B and C are partially miscible with one another. b1c1 ,b2c2 are tie – lines.

Tabular column:

Note down the densities of three components at room temperature.

 10

A 100 %

Weight fraction Weight fraction

of B of A

c2

b2 c1

b1

B 100 % C 100 %

Weight fraction
of A EXPERIMENT
FOUR

EXCESS PROPERTY DETERMINATION

AIM:

To determine the partial molar volume and excess molar volume of a non-ideal
mixture at atmospheric temperature and pressure.

PRINCIPLE:

Excess functions are thermodynamic properties of solutions which are in excess of

those if an ideal solution at the same temperature, pressure and composition. If M represents the
molar value of any extensive thermodynamic property (eg. V,U,H,S,G etc.,), then an excess
property ME is defined as the difference between the actual property value of a solution and the
value it would have as an ideal solution at the same temperature, pressure and composition.

ME = M - Mid

If the thermodynamic property is the volume then the excess volume is given by

VE = Vi - Viid

Excess functions may be positive or negative. When the excess property (eg.
Volume) of a solution is greater than zero, the solution is said to exhibit positive deviations from
ideality whereas if it is less than zero the deviations from ideality are said to be negative. M i is
 11

the pure component molar thermodynamic property of a component forming mixture. For a
component in an ideal solution , the partial molar property M i is same as the pure component
molar property Mi. If the mixture behaves as non-ideal , then the partial molar property that is
formed by mixing two or more components. The components may be ideal and the resulting
solution may be ideal or non-ideal. The excess property determination is very much useful in
determining the property of mixing and is further used in solution property determination.

PROCEDURE:

SYSTEM: METHANOL – WATER

Prepare different compositions of methanol- water mixture by taking methanol (say

0, 2, 4, 6, 8, 10 cc) and make them to 10 cc by adding water. Before mixing , weigh the
components individually. Shake well. Pipette out 5 cc of mixture into a specific gravity bottle
and find its weight. Repeat this for other mixtures also.

Pipette out 5 cc of pure components as well into the specific gravity bottle and find
its weight. Determine the density of the pure component as well as for the above mixtures; from
this calculate specific volume. Find the moles of methanol and water. Find the mole fractions.
The average molecular weight is found by using the formula.

Avg.mol.weight. = (x1M1)+(x2M2)

Where :

x1,x2 – mole fraction of components 1 &2

M1,M2 – molecular weights of components 1 &2

Find the molar volume by multiplying specific volume and average molecular
weight of individual mixtures.

A graph of molar volume vs. composition of the methanol is to be drawn. From the
graph at different composition (say 0.1, 0.2, . . . , 1.0) determine partial molar property by

TANGENT INTERCEPT METHOD:

At each of the selected liquid compositions find V´ 1E using the equations.

V´ 1E =V́ 1– V1 and

Where:

V 1,V 2: partial molar volume of component 1 & 2; at specified x1,x2.

 12

V1, V2: pure component molar volume of 1 & 2.

Find the excess volume of mixture using the formula.

VE = x1V 1E + x2V 2E

Draw a graph between VE, V 1E,V 2E and x1 the composition of methanol. From the
graph find the partial molar excess volume at infinite dilution.

RESULT:

At atmospheric temperature and pressure

V 1E∞ = ____________ cc/mole.

V 2E∞ = ____________ cc/mole.

TABULATION

TABLE 1:

T= oC, P= 1 atm, methanol-1, water-2, M1=32 gm /mol, M2 = 18 gm/mole.

Volume Volume Weight Weight Weight n1= n2= n= x1= x2=

of of of 5 cc
Of Of w1 w2 n1+n2 n1 n2
methanol water of
mixture M1 M2 n n
Methanol water (g) w1 (g) w2 (g) w
(cc) (cc)

0 10

2 8

4 6

6 4

8 2

10 0

TABLE 2:
 13

Specific volume = Avg. mol. Wt. = V molar volume =(Specific

volume)*avg m.weight
5cc/w gm (x1M1)+(x2M2) (gm/gm {cc/mole.)
mole.)

TABLE 3:

V1= _______ cc/mole., V2 = ________ cc/mole.

x1 x2 V1 V2 V 1E = V 1 – V1 V 2E = V 2 – V2 E
VE = x1V 1 + x2

V 2E

EXPERIMENT
FIVE

VAPOR COMPRESSION REFRIGERATION TEST RIG

 14

AIM:
To determine the COP (Co-efficient of Performance) and the power requirement for the
given vapor compression refrigeration rest rig.

PRINCIPLE INVOLVED:
Refrigeration is best known for its use in the air conditioning of buildings; in the
treatment, transportation, preservation of foods and beverages in large-scale industries. It is used
in the manufactures of ice and dehydration of gases; lubricating oil purification; low temperature
reactions; separation of volatile hydrocarbons in the petroleum industry and also in gas
liquefaction.
Refrigeration implies the maintenance of a temperature below that of the surroundings.
This needs continuous absorption of heat at a low temperature level, accomplished by
evaporation of a liquid in a steady flow processes. The vapor formed may be returned to its
original liquid state for re-evaporation in two ways.
1. It is simply compressed and then condensed.
2. It is absorbed by liquid of low volatility, and then evaporated at higher pressure.
A liquid evaporating at constant pressure provides a means for heat absorption at constant
temperature. Condensation of the vapor, after compression to higher pressure, provides for the
original state by an expansion process. This can be carried out in turbine from which work is
constitutes the cycle as shown in the figures 1 and 2.
The cycle is equivalent to the Carnot cycle; except that superheated vapor from
compressor (point 3 in fig) must be cooled to its saturation temperature before condensation
begins.
On the basis of a unit mass of fluid, the heat absorbed in the evaporator is
|Qc| = H2-H1
(Assuming small changes in the potential and kinetic energy are neglected)
Heat rejected in the condenser is

|QH|= H3-H4

But W= |QH|- |Qc| = (H3-H4)-(H2-H1)

Co-efficient of performance (COP) is ω

¿= H 2−H 1
ω = ¿ Q c∨ ¿
W (H 3−H 4 )−(H 2−H 1)
 15

Design of evaporator, compressor, condenser and auxiliary equipments requires

knowledge of the rate of circulation of refrigerant ṁ

ṁ=¿ Q c∨ ¿ ¿
( H 2−H 1)

PROCEDURE:
1. Identify the parts namely compressor, condenser, expansion device and evaporator.
Study the piping arrangement and identify the pressure connections and temperature
connections.
2. Fill up the evaporator up to a known level with a known quantity of water.
3. Open the valves V1, V3, V4 and close the other valves namely V 2, V6. Switch off
the solenoid valve. Ensure that flow is through the capillary tube.
4. Switch on the power supply for the fan and compressor.

Precaution: (The voltmeter reading should not exceed 230 volts and ammeter reading
should exceed three amps)
5. Run the system for sometime to attain steady state condition.
6. At steady state, change the water in the evaporator with a known volume of
water, start stopwatch, note the time of starting and initial temperature of water
in evaporator.
7. Run the experiment for 20 min
8. Meanwhile not pressure gauge reading P1, P2, P3 and P4
9. Note the temperature indicator readings T1, T2, T3 and T4.
10. While in operation, note down the time for 10 revolutions in the energy meter reading
for fan and compressor. Note down the energy meter constants.
11. At 20 min, stop the operation and note down the final temperature of water in the
evaporator.
12. Tabulate all the readings. Repeat the procedure for expansion through solenoid valve
by opening valves V1, V2 and close the valves V6, V3, V4.

CALCULATION:
From P-H chart, obtain H1, H2, H3 and H4 corresponding to (P1, T1), (P2, T2), (P3, T3),

(P4, T4). Also obtain saturation enthalpiesH o1, H o2 , H o3and H o4

● Find |Qc| and |QH|

● Find total work W and COP
 16

● Also calculate the rate of circulation of refrigerant ṁ

● From the energy meter reading, Calculate the work done the on the fan and compressor
H o4−H 3o
● Calculate COPideal= o
H 1−H o4
Where H o1 , H o3and H o4 indicates the saturation enthalpies at point 1,3 and 4.

● Also, calculate
H 4−H 3
COPactual =
H 1−H 4

T i +273.15
COPcaronot = Ti
T o −T i

Where T i = Initial temperature of water in evaporator in OC.

T O= Final temperature of water in evaporator in OC.

COP actual
ηcycle =
COPidal

RESULT:
COPactual =
COPcaronot =
COPideal=
ηcycle =¿

ṁ=¿

Total work =

EXPERIMENT
 17

SIX

COTTRELL BROWN BOILING POINT APPARATUS

ISOBARIC VLE DATA (T-X1-Y1)
AIM:
To draw the T-X1-Y1 diagram (generation of isobaric VLE data) for the given system at
atmospheric pressure and to determine the behavior of the mixture.

PRINCIPLE:
The Cottrell Brown boiling point apparatus is used to determine the equilibrium
temperature attained by a liquid mixture having a fixed composition at a constant pressure of 1
atm absolute. The apparatus is so designed that the vapor composition determination is difficult
(small amount of samples can be obtained, from which it is impossible to determine the
composition). Hence a rigorous procedure is employed to determine the vapor composition.
T-X1-Y1 diagram (ISOBARIC VLE data) is useful for the design of different columns
used for separating the components forming the mixtures.
If the resulting solution formed by mixing two components is an ideal solution, Raoult’s
law can be used (yiP = xiPisat)
If it is a non ideal solution, modified Raoult’s law is used which is given as
yiP = xiPisatγ i
where
yi= mole fraction of component ‘i’ in the liquid phase.
xi= mole fraction of component ‘i’ in the liquid phase.
P = Total pressure, atm
Pisat = Vapor pressure for component ‘i’ at given temperature (usually obtained
from literature or by Antonnie’s equation), atm
γ i = Activity coefficient of component ‘i’ due to non-ideality

PROCEDURE:
 18

SYSTEM:

1 2

Acetone Water

Methanol Water

Acetone Benzene

Methanol Toluene

Various mixtures of the given system were prepared. The equilibrium temperatures for
pure components were determined using the apparatus. The equilibrium temperatures for the
different mixtures were determined and in each case liquid samples were withdrawn and
analyzed to get x1 and x2, the mole fraction of components 1&2 in the liquid phases.
If possible, withdraw vapor samples and analyse. If not, rigorous procedure is used to get
vapor composition y1 and y2.
TABULATION:

Mole fraction of component 1 Mole fraction of component 2 Equilibrium temperature,toC

in liquid phase, x1 in liquid phase, x2

1 0 t1sat

0 1 t2sat

CALCULATION:
a) Determine P1sat and P2sat in atm at different temperatures, toC and given P=1 atm
b) Calculate
x1 Psat
1
b1 = and
P
x2 Psat
2
b2 =
P
 19

y 1 x 1 Psat
1
y 2 x 2 Psat
2
{b1= ¿ and b2= ¿
γ1 P γ 2 P

b2 (1−b2)
c) Calculate B=
b1 (1−b1)
d) Draw a graph of lnB Vs x1
Prof.Dr.PL. SABARATHINAM showed that

ln ln γ ∞1 =ln ln B

ln ln1/ γ ∞2 =ln ln B

Find ln ln γ ∞1 ∧ln ln γ ∞2 from the graph of ln ln BVs x1

e) If margule’s law is applicable, then

ln ln γ ∞1 =¿ A12, ln ln γ ∞2 =¿ A21

If VanLaar’s law is applicable, then ln ln γ ∞1 =A '12, ln ln γ ∞2 =A '21

Find the constants A12 , A 21 or A'12, A'21
GE GE
f) Then determine =x 1 ln ln γ 1 + x 2 ln ln γ 2 and plot a graph of Vs x 1. If this is a
RT RT x x 1 2

RT x x
straight line, Margule’s equation is applicable. If not plot a graph of Vs x 1 and if
1 2

GE
this is a straight line, VanLaar equation is applicable. Then use appropriate γ 1∧γ 2 for
further calculation.
γ 1 x 1 Psat γ 2 x 2 Psat
y
g) Find 1 ¿ 1
y
, 2¿ 2
Ensure that y 1 + y 2=1
P P.
From the values of T, x 1 , y 1 , T, x 2 , y 2 plot graphs of T −x 1− y 1 and T −x 2− y 2 at given P=1
atm
h) From the values of γ 1∧γ 2the nature of solution formed from the components 1 &2 can be
predicted.

RESULT:
T-X-Y diagram for the given system was drawn and the characteristics of the system
were studied.

TABULATION:

x1 x2 tOC Psat
1 Psat
2 x1 Psat
1 x2 Psat
2
b2 (1−b2)
b1=
P P b1 (1−b1)
 20

Atm atm

1 0 t1sat Psat
1 =1 Psat
2 =

0 1 t2sat Psat
1 = Psat
2 =1

If Margule’s equation applicable ln ln γ ∞1 =¿ A12, ln ln γ ∞2 =¿ A21;

x1 x2 γ1 γ2 GE GE
=x 1 ln ln γ 1 + x 2 ln ln γ 2
RT RT x x
1 2

If VanLaar equation applicable γ ∞1 =A '12, ln ln γ ∞2 =A '21

x1 x2 γ1 γ2 GE RT x x
=x 1 ln ln γ 1 + x 2 ln ln γ 2 1 2

RT GE
 21

P = 1 bar, T = 298 K, Calculate the partial molar volumes of methanol

x mole 0 0.114 0.197 0.249 0.495 0.692 0.785 0.892 1

fraction
of
methano
l

V x 103 0.0181 0.0203 0.0219 0.023 0.0283 0.0329 0.0352 0.0379 0.0407
m3/mol

V = 0.004 x2 + 0.0187x + 0.0181

EXPERIMENT
SEVEN

OTHMER VLE STILL

Margules (or) VanLaar constants determination
 22

Thermodynamic consistency test for T-x1-y1 data obtained in the laboratory

AIM:
To determine the Margule’s constants (or) VanLaar constants for the given binary
system; to subject the T-x1-y1 data obtained in the laboratory for thermodynamic consistency test.
PRICIPLE INVOLVED:
Othmer VLE still is used to determine the equilibrium temperature, equilibrium vapor
composition for a binary liquid mixture whose liquid composition is known.
If the solution formed by mixing two individual components behaves as an ideal solution.
Raoult’s law can be used; Otherwise modified Raoult’s law, incorporating activity coefficients
for the components in liquid phase for non-ideality can be used. For such systems the constants
in Margules or Vanlaar equation have to be determined.
Moreover the isobaric VLE data (T-x1-y1 data) generated in the laboratory for such a
binary non-ideal mixture should be subjected to thermodynamic consistency test before using
those data for design purposes.
The thermodynamic consistency test is basically derived from Gibb’s Duhem equation
and modified Raoult’s law. Hence application of this method is very important for any chemical
engineer.
PROCEDURE:
SYSTEMS:

1 2

Acetone Water

Methanol Water

Acetone Benzene

Methanol Toluene

The equilibrium temperature (ie., True boiling point) for the pure components 1&2 were
obtained. A mixture of approximately 25cc of component 1 and 25cc of component 2 was taken
in a round bottom flask and the assembly was arranged in order. Cold water was circulated
through the condenser. The mixture was heated thoroughly. After equilibrium was established
(indicated by a constant reading in the thermometer), The heating was stopped and contents were
allowed to cool to room temperature. The liquid and vapor samples were collected and analysed
 23

(for analytical purpose, a calibration chart for density of the mixture Vs composition was drawn
previously). This enable us to know x1, y1 and toC, equilibrium temperature of the mixture.
The procedure was repeated for different mixtures and for each mixture x 1, y1 and toC
were obtained and tabulated as follows.

toC Density of x1 x2 Density of y1 y2

liquid vapor
sample sample
gm/cc gm/cc

Boiling 0 1 0 1
point of 2=
o
C

Boiling
point of 1=
o
C
1 0 1 0

At these temperatures, Psat sat

1 and P2 were determined using Antonnie’s constants the particular

components 1&2.
Calculate γ 1∧γ 2at given P=1 atm by using the relation

y1 P y2 P
γ1¿ sat , γ2 ¿
x1 P 1 x 2 Psat
2

Using γ 1∧γ 2

Calculate

GE
=x 1 ln ln γ 1 + x 2 ln ln γ 2
RT
 24

GE
Draw a plot of Vs x 1. If linear Margule’s equation is applicable. If not , draw a plot of
RT x x 1 2

RT x x
1
Vs x 1 and if this is linear then VanLaar’s equation is applicable.
2

GE

After ensuring the applicability of any one of the equation, draw a graph of ln ln γ 1 Vs x1 and find
ln ln γ ∞1 ∧ln ln γ ∞2 from the graph. From ln ln γ ∞1 ∧ln ln γ ∞2 , Find the constants A12 , A 21 or A'12, A'21.
γ1
Draw a graph of ¿ Vs x1
γ2

If the area under the graph is zero, the data is consistent, otherwise inconsistent. Then the data
which are inconsistent has to be checked once again for consistency.

Thermodynamic consistency test

1
γ1
The equation ∫ ❑ ¿ dx=0 is used for thermodynamic consistency test at constant T&P.
0 γ2

Here constant P data (isobaric VLE data T-x-y data) is subjected to this test. A plot of
γ1
¿Vs x1 will be a curve so that positive area and negative area will be one and the same.
γ2
Otherwise some data may be inconsistent. Check those data for consistency.

RESULT:
Constants of Margule’s or VanLaar were found to be

A'12=¿ A12=¿

A12=¿ A21=¿

The data generated in the laboratory was found to be consistent/ inconsistent

The system is a non ideal liquid binary mixture showing positive/negative deviation from
ideality.
TABULAR COLUMN:

Density of x1 x2 Density of y1 y2 Psat

1
liquid vapor
mixture mixture At toC mmHg
cc/gm
Cc/gm
 25

Psat
1
y1 P y2 P GE ln ln γ 1 ln ln γ 2 γ1
γ 1= sat
γ 2= sat
¿
x1 P 1 x2 P 2
RT γ2
at toC
mmHg

EXPERIMENT
EIGHT

AIR-WATER HEAT PUMP

AIM:
To determine the performance characteristics of the Air-water Heat-Pump test rig and to
find the power requirement of the unit for winter heating.
PRINCIPLE INVOLVED:
The heat pump, a reversed heat engine, is a devise for heating houses and commercial
buildings the winter and cooling them during the summer. In the winter it operates so as to
absorb heat from the surroundings and reject heat into the building. Refrigerant is evaporated in
coils placed underground or in the outside air, and the vapor is compressed for condensation by
air or water, used to heat the building at temperature above the required heating level. The
operating cost of the installation in the cost of electric power to run the compressor. If the unit
¿
has a coefficient of performance, ¿ Qc ∨ W =4 ¿, the heat available to heat the house |QH| is equal
to five times the energy input to the compressor. Any economic advantage of the heat pump as a
heating devise depends on the cost of electricity in comparison with the cost of fuels such as oil
and natural gas.
 26

The heat pump also serves for air conditioning during the summer. The flow of
refrigerant is simply reversed, and heat is absorbed from the building and rejected through
underground coils or to the outside air.
PROCEURE:
1. Identify the parts of unit Viz., the compressor, condenser, expander and fan Identify the
piping arrangements.
2. Valve Vw1 is partially opened and Vw2 ,Vw4 and Vw5 should be closed. Valve Vw3 should be
opened gradually to vary the flow rate of water flowing through the water- cooled
condenser.
3. The following valves in the refrigerant flow line has to be opened; V 1, V2, V4, V7,V9 and
V10. The flowing valves in the refrigerant flow line has to be closed; V3, V5, V6, and V8.
4. Water should be allowed to flow through the water-heated condenser in small quantity
through the valve Vw3. The valve Vw1 should be opened slowly so that re-circulation of
water is established.
5. The system is switched on. The water pump, fan and compressor is switched on.
6. After the system reaches steady state (indicated by a constant outlet temp of water from
the condenser) the pressures P1, P2, P3 and P4, Temperatures T1, T2, T3 and T4 are noted.
The condenser water inlet temp and outlet temp are recorded as T5 and T6. The flow rate
of water through the condenser is note down.
The time for 5 revolutions in the energy maters of fan and compressors are noted. The
voltmeter and ammeter readings are also noted. The energy meter constants are also noted.
7. The cold water flow is varied and for each flow rate the readings were noted. The
readings were tabulated.
 27

P4, T4 P3, T3

Cold water
Cold water
Cold water Time for
Time
5 for 5 rev in
flow inlet outlet rev in compressor
rate temp temp fan energy
cc/sec T5 , T6 , energy meter sec
o o
C C meter
sec
 28

CALCULATION:
COP ideal, actual and carnot may be determined. The rate of circulation of refrigerant is
also determined. Heat absorbed in the water-cooled condenser is determined. The total work
requirement is also determined.

RESULTS:
COPactual =
COPidal =
COPcarnot =
Rate of circulation of refrigerant =
Rate of circulation of condenser =
Total power requirement =