I.

Introduction

The experiment aims to determine the partial molar volumes of different concentrations of Sodium
Chloride (NaCl) solution. The verification of the Debye-Huckel Theory and comparison of the accuracy of the
method of apparent volume with the method of intercepts in the estimation of partial molar volumes will be done.
This experiment is significant for:__________________________________.
In the experiment constant pressure is assumed and temperature is assumed.

II. Theory
It is central in solution thermodynamics to study and define mathematically the behavior of individual
species as they exist in solution – partial properties. (Smith, 2005)
For any closed system, the relation of the total Gibbs energy with pressure and temperature:
𝑑(𝑛𝐺) = (𝑛𝑉)𝑑𝑃 − (𝑛𝑆)𝑑𝑇
Equation 1
where n is the total number of moles of the system. This can be applied primarily to single phase fluids in a closed
system such that no chemical reactions occur in the system hence, composition is constant and therefore:
𝜕(𝑛𝐺) 𝜕(𝑛𝐺)
[ ] = 𝑛𝑉 [ ] = −𝑛𝑆
𝜕𝑃 𝑇,𝑛 𝜕𝑇 𝑃,𝑛
Equation 2 Equation 3
The number of moles of all chemical species are held constant and denoted by the subscript n in the
partial derivatives above. (Smith, 2005)
Making equation 1 more general applying to single-phase, open system and nG as a function of the
numbers of moles of the chemical species:
𝑛𝐺 = 𝑔(𝑃, 𝑇, 𝑛1 , 𝑛2 , … , 𝑛𝑖 , … )
Equation 4
Where ni is the number of moles of species i. The total differential of nG is then: (substituting equations 2
and 3)
𝜕(𝑛𝐺) 𝜕(𝑛𝐺) 𝜕(𝑛𝐺)
𝑑(𝑛𝐺) = [ ] 𝑑𝑃+ [ ] 𝑑𝑇 + ∑ [ ] 𝑑𝑛𝑖
𝜕𝑃 𝑇,𝑛 𝜕𝑇 𝑃,𝑛 𝜕𝑛𝑖 𝑃,𝑇,𝑛
𝑖 𝑗

Equation 5
The derivative in the final term is defined as the chemical potential, 𝝁𝒊 , of species i in the mixture:
𝜕(𝑛𝐺)
𝜇𝑖 ≡
𝜕𝑛𝑖
Equation 6
This definition of the chemical potential as the derivative of nG with respect to ni suggest that other
derivatives of this kind should prove useful in solution thermodynamics. (Smith, 2005) Thus, we define partial
̅ 𝒊 of species i in the solution as:
molar property 𝑴
 𝜕(𝑛𝑀)
̅𝑖 ≡ [
𝑀 ]
𝜕𝑛𝑖 𝑃,𝑇,𝑛
𝑗

Equation 7
Therefore, equation 6 will be:
𝜇𝑖 = 𝐺̅𝑖
Equation 8
which means that the chemical potential of a species in solution is the partial molar Gibbs energy.
Partial molar property is a response function or the measure of the response of total property nM to the
addition of a differential amount of species i to a finite amount of solution at constant P and T. M can be any
̅ 𝒊 can be any of the corresponding partial properties
solution properties (V, U, H, S, and G) while 𝑴
̅𝒊, 𝑼
(𝑽 ̅ 𝒊, 𝑯 ̅𝒊 , 𝒂𝒏𝒅 𝑮
̅ 𝒊, 𝑺 ̅ 𝒊 ). Central to the field of applied solution thermodynamics, the partial-property concept

implies that a solution property represents a “whole,” i.e. the sum of its parts as represented by partial properties
̅𝑖 of the constituent species. (Smith, 2005) The major concern of this experiment is the use of the partial molar
𝑀
volume:
𝜕(𝑛𝑉)
𝑉̅𝑖 ≡ [ ]
𝜕𝑛𝑖 𝑃,𝑇,𝑛
𝑗

Equation 9
In other words, 𝑉̅𝑖 equals the partial derivative of V with respect to the number of moles of i with
temperature, pressure, and the number of moles of all other components held constant. If temperature and
pressure are held constant, then

𝑑𝑉 = ∑ 𝑉̅𝑖 𝑑𝑛𝑖
𝑖

Equation 10

In this experiment it is an aim to look for the partial molar volume of sodium chloride (NaCl) in NaCl-water
solution. In this case Equation 10 becomes

𝑑𝑉 = 𝑉̅𝑁𝑎𝐶𝑙 𝑑𝑛𝑁𝑎𝐶𝑙 + 𝑉̅𝑤𝑎𝑡𝑒𝑟 𝑑𝑛𝑤𝑎𝑡𝑒𝑟

Equation 11

where

𝜕(𝑉) 𝜕(𝑉)
𝑉̅𝑁𝑎𝐶𝑙 = [ ] 𝑎𝑛𝑑 𝑉̅𝑤𝑎𝑡𝑒𝑟 = [ ]
𝜕𝑛𝑁𝑎𝐶𝑙 𝑃,𝑇,𝑛 𝜕𝑛𝑤𝑎𝑡𝑒𝑟 𝑃,𝑇,𝑛
𝑤𝑎𝑡𝑒𝑟 𝑁𝑎𝐶𝑙

Equation 12 Equation 13
The integration of Equation 11 at constant temperature and pressure from nNaCl and nwater equal to zero to
some final values of nNaCl and nwater , gives

𝑉 = 𝑉̅𝑁𝑎𝐶𝑙 𝑛𝑁𝑎𝐶𝑙 + 𝑉̅𝑤𝑎𝑡𝑒𝑟 𝑛𝑤𝑎𝑡𝑒𝑟

 Equation 14
Equation 14 gives the impression that 𝑉̅𝑁𝑎𝐶𝑙 and 𝑉̅𝑤𝑎𝑡𝑒𝑟 are the volumes of one mole of the solute and
water respectively; however Equations 12 and 13 show that this is not true. These equations show
that 𝑉̅𝑁𝑎𝐶𝑙 and 𝑉̅𝑤𝑎𝑡𝑒𝑟 are the rates at which the volume of the whole solution changes as the moles of solute or of
water are changed while temperature, pressure, and the moles of the other are held constant.
To solve for the partial molar volume of NaCl in the experimental setup, the following calculation should
be made. With reference to Equation 14, let 𝑉̅𝑤𝑎𝑡𝑒𝑟 = 𝑉̃𝑤𝑎𝑡𝑒𝑟
0
where 𝑉̃𝑤𝑎𝑡𝑒𝑟
0
is the molar volume of pure water
(equal to 18.069cm3mol-1 at 25.00 oC) and define the apparent molar volume φ of the solute. The solution can be
assumed to contain 1000 g (55.51 mole) of water and m (molality) mole of solute.(Shoemaker,____) Equation 14
will now be:
𝑉 = 𝑚𝜙 + 𝑛𝑤𝑎𝑡𝑒𝑟 𝑉̃𝑤𝑎𝑡𝑒𝑟
0

Equation 15

𝑉 = 𝑚𝜙 + 55.51𝑉̃𝑤𝑎𝑡𝑒𝑟
0

Rearranging,
(𝑉 − 55.51𝑉̃𝑤𝑎𝑡𝑒𝑟
0
)
𝜙=
𝑚
Equation 16
Now
1000 + 𝑚𝑀𝑊𝑁𝑎𝐶𝑙
𝑉= 𝑐𝑚3
𝑑
Equation 17
and
1000
𝑛𝑤𝑎𝑡𝑒𝑟 𝑉̃𝑤𝑎𝑡𝑒𝑟
0
= 𝑐𝑚3
𝑑𝑜
Equation 18
where d is the density of the solution and do is the density of pure solvent, both in units of gcm-3, and MWNaCl is the
molecular weight of NaCl in grams per mole. Substituting Equations 17 and 18 into equation 16, we obtain
1000 + 𝑚𝑀𝑊𝑁𝑎𝐶𝑙 1000
( − )
𝑑 𝑑𝑜
𝜙=
𝑚
And by further simplifying, we have:
1 1000 𝑑 − 𝑑𝑜
𝜙= [𝑀𝑊𝑁𝑎𝐶𝑙 − ( )× ]
𝑑 𝑚 𝑑𝑜
1 1000 𝑊 − 𝑊𝑜
𝜙= [𝑀𝑊𝑁𝑎𝐶𝑙 − ( )× ]
𝑑 𝑚 𝑊𝑜 − 𝑊𝑒
Equation 19
 In equation 19, We: empty mass of pynometer, Wo: mass of pycnometer when filled to the mark with pure
water, W: mass of pycnometer when filled with solution. Equation 19 is preferred over the equation above it for it
is not easy to determine the densities to the high precision. (Shoemaker
With the application of equations 14 and 15 to the definition of partial molar volume (Equation 9), the
definition becomes:
𝜕(𝑛𝑉) 𝜕𝜙
𝑉̅𝑁𝑎𝐶𝑙 = [ ] =𝜙+𝑚
𝜕𝑛𝑖 𝑃,𝑇,𝑛 𝜕𝑚
𝑤𝑎𝑡𝑒𝑟

Equation 20
But for solutions of simple electrolytes, it has been found that many apparent molar quantities such as φ
vary linearly with √𝑚, even up to moderate concentrations. (Shoemaker_____) The Debye-Hückel theory for dilute
solution supports this behavior. Since
𝜕𝜙 𝑑𝜙 𝑑 √𝑚 1 𝑑𝜙
= =
𝜕𝑚 𝑑 √𝑚 𝑑𝑚 2√ 𝑚 𝑑 √ 𝑚
Equation 21
We obtain the partial molar volume of NaCl from equation 20 and 21:

√𝑚 𝑑𝜙 3√𝑚 𝑑𝜙
𝑉̅𝑁𝑎𝐶𝑙 = 𝜙 + = 𝜙𝑜 +
2 𝑑 √𝑚 2 𝑑 √𝑚
Equation 22
where φ0 is the apparent molar volume extrapolated to zero concentration. Now 𝑉̅𝑁𝑎𝐶𝑙 can be obtained from the
slope and y intercept of φ vs √𝑚 plot’s best fit straight line.

̅ 𝒊 and 𝑽
Finding relationships among partial molar properties (specifically 𝑮 ̅ 𝒊 ) is essential in this

experiment. Applying equations 2, 3, 6 and 8 to equation 5 we now have:

𝑑(𝑛𝐺) = (𝑛𝑉)𝑑𝑃 − (𝑛𝑆)𝑑𝑇 + ∑ 𝐺̅𝑖 𝑑𝑛𝑖

𝑖
Equation 23

Execution of the criterion of exactness, yields the Maxwell relation,

𝜕𝑉 𝜕𝑆
( ) = −( )
𝜕𝑇 𝑃,𝑛 𝜕𝑃 𝑇,𝑛
Equation 24
and including the two equations:
𝜕𝐺̅𝑖 𝜕(𝑛𝑉) 𝜕𝐺̅𝑖 𝜕(𝑛𝑆)
( ) =[ ] ( ) =[ ]
𝜕𝑃 𝑇,𝑛 𝜕𝑛𝑖 𝑃,𝑇,𝑛 𝜕𝑇 𝑃,𝑛 𝜕𝑛𝑖 𝑃,𝑇,𝑛
𝑗 𝑗

Equation 25 Equation 26
Taking to account equation 7, Equation 25 and 26 can also be expressed as:
 𝜕𝐺̅𝑖 𝜕𝐺̅𝑖
( ) = 𝑉̅𝑖 ( ) = −𝑆𝑖̅
𝜕𝑃 𝑇,𝑥 𝜕𝑇 𝑃,𝑥

Equation 27 Equation 28
The above equation allow calculation of the effects of P and T on the partial Gibbs energy (or chemical
potential). (Smith, 2005)