DURBAN UNIVERSITY OF TECHNOLOGY

FACULTY OF APPLIED SCIENCES

DEPARTMENT OF CHEMISTRY

EXPERIMENT 4:

EXCESS MOLAR VOLUME FOR BINARY

SYSTEM

STUDENT NAME : KUNENE M

STUDENT NUMBER : 21328199
SUBJECT : PHYSICAL CHEMISTRY IV

LECTURE : PROF DEENADAYALU

AIM: Is to determine the binary excess molar volume from experimental density measurements.

The results are to be interpreted in terms of intermolecular interactions.

Theory:

No real solution is ideal and real solutions will differ from an ideal solution based on the
intermolecular interactions. The concept of excess function is used to define the difference
between an intensive property value for a real solution and an ideal solution. The excess, real and
ideal property must all be at the same temperature, T, pressure, p, composition, (𝑥𝑖 ) and state.

In general, the excess property can be written as :

𝑓 𝐸 (𝑇, 𝑃, 𝑥𝑖 ) = 𝑓 𝑟𝑒𝑎𝑙 (𝑇, 𝑃, 𝑥𝑖 ) − 𝑓 𝑖𝑑𝑒𝑎𝑙 (𝑇, 𝑃, 𝑥𝑖 )

Where 𝑓 𝐸 , 𝑓 𝑟𝑒𝑎𝑙 and 𝑓 𝑖𝑑𝑒𝑎𝑙 refers to the excess, real and ideal intensive property.

In particular, for the volume intensive property, 𝑣 𝐸 , 𝑣 𝑟𝑒𝑎𝑙 and 𝑣 𝑖𝑑𝑒𝑎𝑙 will be given by this
equation:

𝑣 𝐸 (𝑇, 𝑃, 𝑥𝑖 ) = 𝑣 𝑟𝑒𝑎𝑙 (𝑇, 𝑃, 𝑥𝑖 ) − 𝑣 𝑖𝑑𝑒𝑎𝑙 (𝑇, 𝑃, 𝑥𝑖 )

The excess property provides a way to determine how a real mixture deviates from an ideal
solution. In general, an excess property may be positive, negative or zero.

In this work density, p, will be measured and to determine the excess molar volume, together
with the mass weighted, m.

Apparatus :

 Syringe
 Digital vibrating – tube density meter and speed of sound analyzer (Anton Paar
Densitometer)
 Conical flask with caps

Chemicals:

 Ethanol (drying solution)

 De – ionized water
 Toluene
 Cyclohexane
 Acetone (drying solution)
 Procedure:

Data:
Table 1. Masses weighed to prepare binary solutions with mole fractions

Molar Molar Mole

Mass Mass mass M1 mass M2 Mole Mole Total Refraction Mole
m1 (g) m2 (g) (g/mole) (g/mole) m1 m2 mole x1 Refractionx2

0.0000 10.0000 84.1600 92.1400 0.0000 0.1085 0.1085 0.0000 1.0000

2.0057 8.0030 84.1600 92.1400 0.0238 0.0869 0.1107 0.2152 0.7850

4.0274 6.0131 84.1600 92.1400 0.0479 0.0653 0.1132 0.4231 0.5769

6.0186 4.0091 84.1600 92.1400 0.0715 0.0435 0.1150 0.6217 0.3783

8.0196 2.0320 84.1600 92.1400 0.0953 0.0221 0.1174 0.8118 0.1882

10.0000 0.0000 84.1600 92.1400 0.1188 0.0000 1.1188 1.0000 0.0000

 Mole : n = m/Mm
 Mole fraction : n1 = n1/(n1+n2) and n2 = n2(n1+n2)
 1a. m1 (moles) = m1/M1
 b. m2 (moles) = m2/M2
 c. Total moles = mole m1+ mole m2
 d. mole fraction (x1) = moles m1/ total moles
 e. mole fraction (x2) = moles m2/total moles
 f. x1M1= mole fraction (x1). Mm (M1)

 g. x2M2 = mole fraction (x2) . Mm (M2)

Results :

Calculations

Table 2: Densities of pure component and binary mixtures.

The densities were measured at 250C with an Anton Paar densitometer.

Ρsolutions X1M1 (g/mol) X2M2 (g/mol)

0.8399 18.11 72.32

0.8191 35.61 53.16

0.8025 52.32 34.86

0.7874 68.32 17.34

 P1 = 0.7737
 P2 =0.8608

VmE = (X1M1+X2M2)/ρ – [(X1M1/ρ1) + (X2M2/ρ2)

Table 3

X1M1+X2M2 X1M1+X2M2/ρ X1M1/ρ1 X2M2/ρ2 X1M1/ρ1+X2M2/ρ2 VmE

90.43 107.66 23.41 84.01 107.42 0.2351

88.77 108.37 46.03 61.76 107.79 0.5835

87.18 108.64 67.62 40.49 108.12 0.5229

79.66 101.17 80.55 20.14 100.69 0.4759

Graph 1

excess molar volume vs mole fraction x1

0.7

0.6
y = -1.5168x2 + 1.8215x
0.5
excess molar volume

0.4

excess molar volume

0.3
Poly. (excess molar volume)

0.2

0.1

0
0 0.2 0.4 0.6 0.8 1
molar fraction

Discussion

Cyclohexane and Toluene are non-polar with only London forces, when there were mixed
together there was only one layer. The non-polar molecules the two different liquid are soluble in
each other because of similar properties. Referring to table 2, when a solution of cyclohexane
and toluene was mixed and the ratio was 2:8 the density of a solution was 0.8399g/𝑐𝑚3 and
when the ratio was 8:3 the density became 0.7874g/𝑐𝑚3 this shows that the density of toluene
solution is greater than for a solution of cyclohexane. The increase in the excess molar volume was
due to the bond dissociation due to excess volume of cyclohexane added. There is not much
electronegativity difference between C-H, hence there’s hardly bond polarity. Cyclohexane also has very
little polarity or is rather non polar. The decrease in the excess molar volume was due to the bond
formation in toluene, that was, when more toluene was added in the mixture. Toluene is highly polar than
cyclohexane.

.
Conclusion

The aim of the experiment was achieved as excess molar volumes of two mixtures were
determined and under the experiment it can be fully understood that both mixtures behave the
same and are indeed of the same forces of attraction. Excess molar volume is the value resultants
of the intermolecular interactions that due to the difference between the real and the ideal molar
volumes.

References

 Physical chemistry laboratory manual

 Sime, R.J., “Physical Chemistry: Methods, Techniques and Experiments”, CSU
Publishers, Sacramento CA
 Gonzalez, B., Dominguez, I., E, J., Dominguez, A., J. Chem Eng. Eng. Data 2010, 55,
1003-1011.
 Lainez, A., Rodrigo, M.M., Wilhem, E., Grolier, J.-P.E., J. Chem Eng. Data, 1989, 34,
332-335.
 Fortier, J.-L., Benson, G.C., J. Chem. Thermodynamics, 1977, 9, 1181-1188.
 Department of Chemistry Physical Chemistry IV (Module 401) Practical Manual 2016