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OBJECTIVES

To determine the partial molar volumes of a binary system of liquids from density

measurements.

THEORY

experimentally and so a wide range of extensive thermodynamic properties that define a

system can be explored. Theoretically, any extensive property that defines a system, when

varied with respect to the amounts (ni) of the components that comprise the system at

constant temperature and pressure give rise to interesting intensive properties called

partial molar quantities.

defined based on, say, the ith component of the mixture:

𝜕𝑌

Yi = 𝜕𝑛 𝑖 𝑇,𝑝,𝑛

𝑗

where, Yi is the partial molar quantity based on the ith component, while nj represents the

amount of the rest of the components of the mixture. The most important of these partial

molar quantities is the partial molar free (Gibbs) energy also known as the chemical

potential. In this experiment, however, the partial molar volume is in focus, because it is

much easier to measure experimentally compared to Gibbs energy. The partial molar

volume is a good indicator of non-ideality (similar to the compression factor for real gases)

in mixtures.

It is a common assumption that when two liquids are mixed, the volumes simply add up.

This, however, is only true for ideal solutions—those that are formed from components

that have very similar structures and hence similar forces of attraction operating among

molecules. Very similar forces of attraction lead to minimal expansion or contraction in the

volume of the mixture formed from the components. Any amount of deviation from ideal

behavior is measured in terms of the enthalpy of mixing or a quantity called the partial

molar volume.

Experiment 1: Partial Molar Volumes

𝜕𝑉

VA = 𝜕𝑛 𝐴 𝑇,𝑝,𝑛

𝐵

VA is said to be the partial molar volume of A in a mixture with B. This quantity tells us how

the volume of the mixture changes as the amount of A is varied. For example, for a water-

ethanol system, when one mole of water is added to huge volume of ethanol at 25° the

volume increases by 14 cm3. Hence, it is said that the partial molar volume of water in

ethanol is 14 cm3/mol in this case.

The scenario is different when one mole of water is added to a huge amount of water at

25°C, which gives rise to a volume increase of 18 cm3. This is expected since the

environment that receives the additional one mole of water is also a pool of water

molecules as opposed to a pool of ethanol molecules! Apparently, the partial molar volume

of water in the ethanol mixture will be near 18 cm3/mol if the mixture is largely water, but

its value will be near 14 cm3/mol if ethanol is present in very large amounts compared to

water.

Hence, it can be said that the partial molar volumes of the components of a binary mixture

of A and B vary with the composition of the mixture because the environment of each type

of molecule changes as the composition changes from pure A to pure B.

In this experiment, the partial molar volumes of water and alcohol will be determined by

density measurements using a pycnometer (Figure 1.1).

A pycnometer is a flask with tight-fitting glass stopper with a fine hole through it. A

pycnometer is used for measuring the density of a solution using a reference liquid, such as

water. Essentially, it is the specific gravity that is determined first. This is accomplished by

accurately measuring the mass of the reference liquid using the pycnometer and an

Experiment 1: Partial Molar Volumes

analytical balance. Then, the mass of the liquid is also determined using the same

pycnometer. The specific gravity of the solution is then determined by:

SG = 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑟𝑒𝑓𝑒𝑟𝑒𝑛 𝑐𝑒 𝑙𝑖𝑞𝑢𝑖𝑑

The density values derived from the specific gravity values will be used to determine the

partial molar volumes (such as Vm,A, the molar volume of A). When the partial molar

volumes of the components are already determined, the total volume of the mixture with

known composition can be determined as:

V = nAVm,A + nBVm,B

MATERIALS

Erlenmeyer flasks thermometer

Water alcohol sample (1-propanol, 2-propanol)

Mixture of unknown concentration acetone

PROCEDURE

concentration

1. Calculate the necessary volumes of your alcohol sample and water to prepare 50

mL solutions with the following mole fractions: 0.20, 0.40, 0.60, and 0.80.

2. Record your data in Table 1.1

Table 1.1. Calculated Volumes of Liquids to Be Mixed for Specified Mole Fractions

Sample xB xA VB, cm3 VA,cm3

1

2

3

4

NOTE: xB can be taken here as the mole fraction of your alcohol sample. V B is the calculated volume

of alcohol necessary to prepare the solution based on the xB. The subscript A refers to the solvent,

which is water in this case.

1. Measure the mass of an empty and dry volumetric flask (with the stopper) using

an analytical balance.

2. Add the calculated volume of water for xwater = 0.20 determined in Part A

(Table 1.1) and measure the mass again.

3. Add the alcohol, mix thoroughly, and weigh the sample again.

4. Record all data in Table 1.2.

Experiment 1: Partial Molar Volumes

Sple Empty Flask + Flask + mA*– m0 mB* – mA* mA/MA mB/MB nB/(nA +nB)

flask Soln A A+B

m0 , g mA*, g mB*, g mA , g mB, g nA, mol nA, mol xB

A -- -- -- -- -- -- -- 0

(1)

(2)

(3)

(4)

B -- -- -- -- -- -- -- 1

5. Calculate the actual mole fraction of the solution prepared based on the mass

determinations.

6. Repeat the procedure for the other three solutions. (Don’t forget to label the

flasks).

7. Put all solutions in a thermostated bath for at least 3 minutes before measuring

the densities (Part C).

8. Record the temperature of the bath.

1. Measure the mass of a clean and dry pycnometer.

2. Fill the pycnometer with water and measure its mass.

Important:

a. Always start with a clean and dry pycnometer.

b. Ensure that there are no bubbles every time the pycnometer is filled with a

liquid.

c. The pycnometer should always be filled to the same level. Put the cover while

the excess liquid runs out. Dry the pycnometer using lint-free paper.

d. Ensure that the temperature is the same throughout the measurements.

3. After each measurement, clean the pycnometer using technical acetone.

4. Record observations.

D. Density Measurements

1. Perform measurements of the mass of solutions prepared in Part B using the

same procedure outlined in Part C.

2. Do the same for the pure alcohol sample.

3. Record data in Table 1.3

4. Calculate the densities of each mixture using the formula:

𝑚𝑎𝑠𝑠 𝑜𝑓 𝑚𝑖𝑥𝑡𝑢𝑟𝑒

𝑑=

𝑚𝑎𝑠𝑠 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟

Experiment 1: Partial Molar Volumes

Sple xB xA M Mass of Mass of Density Molar Volume

(from (average) pycnometer liquid (Vm)

Table 1.2) = 1 – xB g/mol + sample, g g g/mL mL/mol

A 0 1.00

(1)

(2)

(3)

(4)

B 1.00 0

1. Plot the density of the mixture against the mole fraction using your data in Table

1.3.

2. Measure the density of your unknown solution and calculate its concentration

(in mole fraction).

Note: The density of your unknown solution can be computed using the average

molar mass of the mixture.

3. Compare the density of your unknown to the literature value. Explain the

difference.

Experiment 1: Partial Molar Volumes

4. Determine the partial molar volume of water and the partial molar volume of the

alcohol at the specified molar concentration (ask your laboratory instructor)

using the tangent method (See Figure 1.2).

5. Compare your values with the molar volumes of the pure compounds. Draw your

conclusions.

POSTLAB PROBLEMS:

1. Calculate the partial molar volume of zinc chloride in 1 molar ZnCl2 solution using the

following data:

Mass percent 2 6 10 14 18

of ZnCl2

Density/ 1.0167 1.0532 1.0891 1.1275 1.1665

g cm–3

2. The partial molar volumes for a carbon tetrachloride (1) – benzene (2) solution at 25°C

are shown in the following table:

X1 0.0 0.3 0.5 0.7 1.0

–1

V1/L mol 0.1793 0.1122 0.1001 0.0983 0.09719

–1

V2/L mol 0.08927 0.09844 0.1064 0.1092 0.1123

(a) What is the molar volume of an equimolar solution?

(b) What is the volume change on mixing 1 and 2 to form one mole of an equimolar

solution?

(c) Account for the value of the molar volume of mixing.

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