Source Partial molar volume is an important thermodynamic phase property.

In general, the partial molar quantity of an extensive thermodynamics property Q is defined as Q Qi ( ) (1) ni p,T ,n j i Where p stands for pressure, T temperature and ni the amount of component i in moles. For a pure phase, partial molar quantities are identical with the molar quantity Q = Q/n. The partial molar volume of a component in a solution is different from the molar volumes of pure phases and changes with the composition. Since the partial molar volume of a phase is a function of its interaction with its environment, it is of interest to study the deviation of partial molar volume from that of the molar volume of the pure phases. In this experiment, a binary solution of sodium chloride and water is considered which for a binary solution V n1V1 n2V2 (2) For an aqueous solution containing m mole of a solute in 1kg (55.51 mole at room temperature) of pure water If one denoted

V 55.51V1 mV2

(3)

~ V1o as the molar volume of pure water, one may define the apparent molar volume

of the solute by the equation By definition

~ ~ V n1V1o n2 55 .51V1o m
V2 ( V d ) n1 , p ,T m n2 dm

(4)
(5)

Also from (3), (4) and (5),

55.1 V1 m V2 55.51 V1o m V1 V1o m 2 d 55.51 dm (6)

d to the dm

Thus, one may determine V1 and V2 by obtaining the tangent plotting of versus m.

However, for solutions of simple electrolytes, it has been found that many apparent

molar quantities, such as, vary linearly with m , even up to moderate concentrations, in agreement with that predicted by the Debye Hckel theory u for dilute solutions. Therefore, it is preferable to plot versus m and from the d best straight line through the points one may determine and o, where o d m is the apparent molar volume extrapolated to zero concentration. Since

d d d m 1 d dm d m dm 2 md m m d 3 m d V2 o 2 d m 2 d m
And

(7) (8)

m m d ~ V1 V1o ( ) 55.51 2 d m

(9)

can be determined by measuring the densities of the solutions and pure water using a pycnometer.

1000 mM 2 cm3 d 1000 ~ n1V1o cm 3 do

(10)
(11)

where d is the density of the solution and do is the density of pure water, both in unit of g cm-3. M2 is the molecular weight of the solute in grams. 1000(d d o ) 1 [M 2 ] (12) d md o
1000(W Wo ) 1 [M 2 ] d m(Wo We ) (13)

where We is the weight of the pycnometer when empty; Wo is the weight of the pycnometer when filled with pure water; W is the weight of the pycnometer when filled with the solution. It is preferable to use equation (13) instead of (12) to avoid the need of calculating the density to high precision for a small difference in d do value.

Partial molar quantities tell us how the properties of solutions change with concentration. We need to know partial molar quantities for all the extensive properties of a solution, including V (volume), G, H, S, and A. Partial molar volume is an important thermodynamic phase property. It is useful for understanding the properties of mixtures. We can find out how much space is occupied by solution 1 vs. solution 2 or how the volume change. Partial molar volume of a solution means how many the volume changes when one mole of it added to another solution. If one adds salt to a full glass of water, the water will not flow over the rim of the glass. According to Millero, it was reported in 1770 that the volume decreases when salts are added to a fixed volume of water. An early theory of electrolyte solutions is that when
salts dissolve in water, they fill the empty space in the liquid. Obviously that theory is not correct. The general reduction in volume on adding a salt to water is attributed to electrostriction, the contraction in volume of the polar solvent around the ions.

When one mole of water is added to a large volume of water, the volume increases by 18cm3 at 25C. Therefore the molar volume of pure water would be reported as 18cm3 mol-1.But some time one mole of water added to a large volume other type of pure solution will result in an increase in different volume(not equal to 18cm3). The reason of the difference is that the volume occupied by a given number of water molecules depends on the identity of the surrounding molecules. The increasing value is regarded as the partial molar volume of water in the solution. In general, the partial molar quantity of an extensive thermodynamics property Q is Q Qi ( ) p,T , n (1) j i ni defined as Where p stands for pressure, T is the temperature ni the amount of component i in moles. For a pure phase, partial molar quantities are identical with the molar quantity Q = Q/n. The partial molar volume of a component in a solution is different from the molar volumes of pure phases and changes with the composition. Since the partial molar volume of a phase is a function of its interaction with its environment, it is of interest to study the deviation of partial molar volume from that of the molar volume of the pure phases. The partial molar is the slope of the plot of the total volume as the amount of J is changed with all other variables held constant:

The partial molar volume, VJ, of any substance J at a general composition, is defined as:

where the subscript n' indicates that the amount of all the other substances is held constant. Method: For a binary mixture,

For volume, one has the following equation,

The partial molar volume of each component, Vj , is likely to be a function of concentration, but it does not depend on the total number of moles. Therefore, one can represent the total volume of the solution by the following equation,
V n1V1 n2V2 (2)

For an aqueous solution containing m mole of a solute in 1kg (1000/18.015 = 55.508 mol at room temperature) of pure water

V 55.51V1 mV2

(3)

Because the partial molar volume of the sample, V2, is also obtained from another quantity, the apparent molar volume of the sample, . The apparent molar volume of the sample, , is calculated with the assumption that the molar volume of the solvent remains constant and any change in volume is due only to the sample. This assumption is false, but it fits a simplified picture of solvent/sample interactions in
~o which only the sample properties change. If one denoted V1 as the molar volume

of pure water, one may define the apparent molar volume of the solute by the equation

~ ~ V n1V1o n2 55 .51V1o m
By definition
V2 ( V d ) n1 , p ,T m n2 dm

(4)

(5)

Also from (3), (4) and (5),

55.1 V1 m V2 55.51 V1o m V1 V1o m 2 d 55.51 dm (6)

d to the plotting dm

Thus, one may determine V1 and V2 by obtaining the tangent

of versus m. However, for solutions of simple electrolytes, it has been found that many apparent molar quantities, such as, vary linearly with m , even up to moderate concentrations, in agreement with that predicted by the Debye Hckel theory for u dilute solutions. Therefore, it is preferable to plot versus m and from the best d straight line through the points one may determine and o, where o is the d m apparent molar volume extrapolated to zero concentration. Since

d d d m 1 d dm d m dm 2 md m

(7)

V2
and

m d 3 m d o 2 d m 2 d m

(8)

m m d ~ V1 V1o ( ) 55.51 2 d m

(9)

 can be determined by measuring the densities of the solutions and pure water using a pycnometer. In the subsequent discussions, the solvent (water) is component 1 and the salt (NaCl) is component 2. One can determine the volume of solution for a fixed amount of one component, n1 mol of solvent, and variable amounts of NaCl. An aqueous solution of
molality, m, contains m moles of salt per 1000 g of water. From the density of this solution, d, in g/mL, one may calculate the volume (in mL) of a solution that contains 1000 g of H2O and m mol of salt of molecular weight MW in g/mol

1000 mM 2 cm3 d

(10)
(11)

1000 ~ n1V1o cm3 do

where d is the density of the solution and do is the density of pure water, both in unit of g cm-3. M2 is the molecular weight of the solute in grams.

1000(d d o ) 1 [M 2 ] d md o

(12) (13)

1000(W Wo ) 1 [M 2 ] d m(Wo We )
where We is the weight of the pycnometer when empty; Wo is the weight of the pycnometer when filled with pure water; W is the weight of the pycnometer when filled with the solution.

It is preferable to use equation (13) instead of (12) to avoid the need of calculating the density to high precision for a small difference in d do value. The partial molar volume is finely understood as the contribution that a component of a mixture makes to the overall volume of the solution. The partial molar volumes of the components of a mixture changes with the composition of the mixture, because the environment of the molecules in the mixture vary with the composition. It is the changing molecular environment and the consequent alteration of the interactions between molecules, that caused the thermodynamic properties of a mixture changing as its composition is altered. The partial molar volume, VJ, of any substance J at a general composition, is defined as:

Which the subscript n' indicates that the amount of all the other substances is held constant. The partial molar is the slope of the plot of the total volume as the amount of J is changed with all other variables held constant: In this experiment, the mixtures are NaCl solutions of different concentration. Once the partial molar volumes of the two components of a mixture at the composition and temperature of interest are known, the total volume of the mixture can be calculated from

The expression may be extended in an analogous fashion to mixtures with any number of components. In general, the partial molar quantity of an extensive thermodynamics property Q is defined as Q Qi ( ) p,T , n (1) j i ni Partial molar volume is an important thermodynamic phase property, where p represent pressure, T stands for temperature and ni is the amount of component i in moles. For a pure phase, partial molar quantities are identical with the molar quantity Q = Q/n. The partial molar volume of a component in a solution is different from the molar volumes of pure phases and changes with the composition. Since the partial molar volume of a phase is a function of its interaction with its environment, it is of interest to study the deviation of partial molar volume from that of the molar volume of the pure phases. Method For a binary mixture V n1V1 n2V2
(2)

For an aqueous solution containing m mole of a solute in 1kg (55.51 mole at room temperature) of pure water

V 55.51V1 mV2

(3)

~o If one denoted V1 as the molar volume of pure water, for NaCl solutions

only contain NaCl and water, one may define the apparent molar volume of the solute by the equation

~ ~ V n1V1o n2 55 .51V1o m
By definition
V2 ( V d ) n1 , p ,T m n2 dm

(4)

(5)

Also from (3), (4) and (5),

55.1 V1 m V2 55.51 V1o m m 2 d V1 V 55.51 dm

o 1

(6)

d Thus, V1 and V2 can be determined by obtaining the tangent dm to the

plotting of versus m. Meanwhile, for solutions of simple electrolytes, it has been found that many apparent molar quantities, such as, vary linearly with
m , even up

to moderate concentrations, which agrees with that predicted by the

Debye Hckel theory for dilute solutions. Therefore, it is more u

convenient to plot versus

m and from the best straight line through

the points by using the least square method, one may determine d m and
o o, where is the apparent molar volume extrapolated to zero

concentration. Since

d d d m 1 d dm d m dm 2 md m

(7)

V2
and

m d 3 m d o 2 d m 2 d m

(8)

m m d ~ V1 V1o ( ) 55.51 2 d m

(9)

 can be found by measuring the densities of the solutions and pure water with the help of a pycnometer.
1000 ~ n1V1o cm3 (11) 1000 mM 2 do 3 V cm (10) d where d is the density of the solution and do is the density of pure water,

both in unit of g cm-3. M2 is the molecular weight of the solute in grams.

1000(d d o ) 1 [M 2 ] d md o

(12) (13)

1000(W Wo ) 1 [M 2 ] d m(Wo We )
where We is the weight of the pycnometer when empty;

Wo is the weight of the pycnometer when filled with pure water; W is the weight of the pycnometer when filled with the solution. It is preferalbe to use equation (13) instead of (12) to avoid the need of calculating the density to high precision for a small difference in d do value.

Sources of error: 1. The pycnometer used may not be clean enough that some water or sodium chloride solution may be still in the pycnometer so that the conc. of the liquid could be different so that the weight may not be accurate. 2. Some of the solution may be loss from the pycnometer so that the weight of the solution and the pycnometer may be deviated from the actual value. 3. The sodium chloride crystals may not be dissolved entirely so that the concentration of the solution may be deviated from the calculated value. 4. Since the density of solution is temperature dependent, the little change in experimental temperature may cause error in density calculation. 5. The contamination of the pycnometer or the solution can result in different weight which is deviate form the actual value. Conclusion and Discussion: After calculation, the results are listed in the following table. -3 -1 Conc. of solution Density (gcm-3) Molality (m) (cm mol ) V1 (cm3)

V 2 (cm3)

3.00 M 1.50 M 0.75 M 0.375 M 0.1875 M The v.s.

1.1144 1.0581 1.0284 1.0134 1.0056

3.1947 1.5457 0.7617 0.3782 0.1885

19.62545 18.30323 17.66101 16.87307 16.64641

17.9453 18.0212 18.0464 18.0550 18.0581

21.5828 19.7671 18.5306 17.6704 17.0669

m graph shows a straight line with equation y = 2.2248x + 15.618.

The equation of the V1 v.s. m graph obtained is y = -0.0381x + 18.071 which shows an inversely proportional relationship between partial molar volume of sodium chloride and its molality to water in the solution. In V 2 v.s. m graph, the equation of the curve is y = 1.4489x + 17.165 which shows an inversely proportional relationship between partial molar volume of water and its mole fraction in the sodium chloride solution. From the experiment data, the result matches with the Gibbs-Duhem equation. Partial molar volume is one of the parameters of partial molar properties. When chemicals are mixed together and allowed to maintain at constant temperature and pressure, there is extensive property between the chemicals. This extensive property can be determined from the partial molar properties such as partial molar volume. This is very useful in study of specific properties of a pure substance or mixing properties of a substances mixture. Partial molar volumes are applicable to real mixtures, including solutions, in which the volumes of the separate, initial components are not additive. This is generally the case, in distinction to the paradigm of ideal mixtures. For real mixtures, there is usually a contraction or expansion on mixing due to changes in interstitial packing and differing molecular interactions. Even so, the total volume is the sum over the partial molar volumes times the numbers of moles, because the volume is a homogeneous function of degree one in the amounts of the various chemical species present. Partial molar quantities can be defined for all the extensive thermodynamic variables in a system. One of the applications of partial molar volume is study of seawater. This is because ocean is the reservoir of water which is important for all organisms and the environment. In seawater, there is not only consists of sodium chloride, but also other minerals and ions. The interactions between water and other molecules can affect the properties of seawater which is closely related to us and the ecosystem.

Therefore, the partial molar volume of seawater can determine the mixing properties of seawater and analyze the quality of seawater. Sources of error: 1. If we rinse the glassware carelessly, the glassware may still have little contaminates and it will affect the result of weighting. 2. The temperature of human being may affect that of the solutions, while the pycnometer was being held. 3. Even that is only a small amount of gas bubbles, it will be an error. 4. Time should be given for weighting. Dont record the weight immediately after putting the sample on the balance. 5. If some liquid adhere the outside of the pycnometer, it is necessary to remove it otherwise we will get a higher weight.

Discussion: For the molarities of each NaCl solution are 3.0106M, 1.5053M, 0.7527M, 0.3763M and 0.1882M, the density of them are 1.1132 g/cm , 1.0578 g/cm , 1.0288 g/cm , 1.0137 g/cm and 1.0061 g/cm
3 3 3 3 3

respectively. The molarities (m) of solution are

3.2121mol/kg, 1.5521 mol/kg, 0.7642 mol/kg, 0.3795 mol/kg and 0.1891 mol/kg respectively. The apparent molar volume of the solute of the solutions are 20.07222 mL/mol, 18.43658 mL/mol, 16.92346 mL/mol, 15.57187 mL/mol and 12.96563 mL/mol respectively. The partial molar volume of D.I. Water V1 for each solutions are 17.8185 mL, 17.9680 mL, 18.0197 mL, 18.0378 mL and 18.0441 mL respectively. The partial molar volume of NaCl V2 for each solutions are 24.7876 mL, 20.9239 mL, 18.2962 mL, 16.4705 mL and 15.1895 mL respectively. The experimental result shows that the partial molar volume of D.I. water (V1) increase while m (molarities) of NaCl solution decrease and the partial molar volume of the NaCl solution (V2) decrease. It matches the Gibbs-Duhem equation.

dQ2 X 1 dQ1 X2
Improvements: 1. It is important for us to use a dried and clean pycnometer in this experiment.

2. 3. 4. 5.

We should not hold the glassware for a long time and make sure the time is given to let the temperature to equilibrate. So make sure the pycnometer is filled thoroughly and ensure no gas bubbles are present in pycnometer by pouring the solutions slowly and carefully. Record it after the weight stop changing. Remove the liquid outside the pycnometer.

Practical applications of partial molar volume: 1. The partial molar volume is important in oceanography and aquatic environmental science as there are a lot of NaCl in the ocean. 2. Partial molar volume is needed in biochemistry for careful calculations of the molecular weights of proteins and nucleic acids using ultracentrifugation. Practical applications of partial molar properties: Partial molar properties are useful because chemical mixtures are often maintained at constant temperature and pressure and under these conditions, the value of any extensive property can be obtained from its partial molar property. They are especially useful when considering specific properties of pure substances and properties of mixing. By definition, properties of mixing are related to those of the pure substance by:

Here * denotes the pure substance, M the mixing property, and z corresponds to the specific property under consideration. From the definition of partial molar properties,

substitution yields:

So from knowledge of the partial molar properties, properties of mixing can be calculated.

Concolution and Disscussion: The partial molar volume of sodium chloride solutions with concentration 3.0M, 1.5M, 0.75M, 0.375M and 0.1875M are 24.7876mL, 20.9239mL,

18.2962mL, 16.4705mL, 15.1895mL while the partial molar volume of D.I. Water with above concentration of NaCl are 17.81849mL, 17.96797mL, 18.01966mL, 18.03776mL, 18.04413mL respectively. They can be calculated form NaCl solution molarity, density of solution, molarity of solution, and apparent molar volume. From the calibration curve one can see that apparent molar volume vary linearly with
m , and Partial

molar volume of D.I. Water vary linearly with molarity of solution m, and partial molar volume of NaCl vary linearly with molarity of solution m. From the calibration curve one can see that there is only small space among the cure and the plots, which means that there exist errors though the accuracy is still high. Partial molar properties are useful because chemical mixtures are often maintained at constant temperature and pressure and under these conditions, the value of any extensive property can be obtained from its partial molar property. They are especially useful when considering specific properties of pure substances and properties of mixing. From knowledge of the partial molar properties, properties of mixing can be calculated. Source of Errors: 1. The body temperature of man may affect that of the solutions, while the pycometer was being held. 2. Very small gas bubbles maybe trapped in the pycometer. 3. The mixture of NaCl and D.I. water may not have enough time to get balance. Improvements: 1. The pycometer could be transported as soon as possible to reduce the time of contact; 2. To ensure no gas bubbles are present in pycometer, the solutions should be poured into the pycometer slowly and carefully. 3. Give enough long time for the mixture to give a balance.