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Water Activity and

Sorption Properties of Food


CRITERIA OF EQUILIBRIUM
 The criterion for thermal equilibrium is equality of
temperatures while the criterion for mechanical equilibrium is
equality of pressures.
 Physicochemical equilibrium is characterized by equality of
chemical potential (μ) of each component.
 The chemical potential determines whether a substance will
undergo a chemical reaction or diffuse from one part of the
system to another.
 The chemical potential of a component in the liquid (L) phase is
equal to that in the vapor (V) phase if vapor and liquid are in
equilibrium:

 Chemical potential is the partial molar free energy and can be


expressed as:
 where G is Gibbs free energy and ni is the moles of
component i . The definition shows that the chemical
potential of a component of a homogenous mixture is equal
to the ratio of the increase in Gibbs free energy on the
addition of an infinitesimal amount of the substance.
 Gibbs free energy is defined as a combination of enthalpy
(H), temperature (T ), and entropy (S):
G = H − TS
 Enthalpy can be expressed in terms of internal energy (U),
pressure (P), and volume (V):
H = U + PV
 For a reversible process in a closed system of constant
composition, the first and second laws of thermodynamics
may be combined to yield:
dU = TdS − PdV
IDEAL SOLUTION—RAOULT’S LAW
 A solution can be defined as ideal if the cohesive forces inside a
solution are uniform.
 This means that in the presence of two components A and B, the
forces between A and B, A and A, and B and B are all the same.
 Equation can be written in terms of partial molar quantities and
since the partial molar free energy is the chemical potential, for
compound A in a solution:

-
where VA is the molar volume of component A in solution
which is the volume divided by the number of moles of A.
 Using ideal gas law and , μA can be related to the partial
vapor pressure by:

 If μ0A is the value of chemical potential when the


pressure is 1 atm,
 Partial vapor pressure of a component, which is a measure of
tendency of the given component to escape from solution into
the vapor phase, is an important property for solutions. For a
solution in equilibrium with its vapor:

 Thus, chemical potential of component A in solution is related


to the partial vapor pressure of A above the solution. Equation
above is true only when vapor behaves as an ideal gas.
 A solution is ideal if the escaping tendency of each component is
proportional to the mole fraction of the component in the
solution.
 The escaping tendency of component A from an ideal solution, as
measured by its partial vapor pressure, is proportional to the
vapor pressure of pure liquid A and mole fraction of A molecules
in the solution. This can be expressed by Raoult’s law as:

where PA is the partial vapor pressure of A, XA is its mole fraction,


and P0A is the vapor pressure of pure liquid A at the same
temperature.

 If component B is added to pure A, vapor pressure is


decreased as:
HENRY’S LAW
 Consider a solution containing solute B in solvent A. If the
solution is very dilute, a condition is reached in which each
molecule B is completely surrounded by component A.
 Solute B is then in a uniform environment irrespective of the
fact that A and B may form solutions that are not ideal at
higher concentrations.
 In such a case, the escaping tendency of B from its
environment is proportional to its mole fraction, which can be
expressed by Henry’s law as:

PB = kXB

where k is the Henry’s law constant. Henry’s law is only


valid for fairly and extremely dilute solutions.
COLLIGATIVE PROPERTIES

 Colligative properties are properties of solutions that


depend upon the ratio of the number of solute particles to
the number of solvent molecules in a solution.
 Vapor pressure lowering, boiling point elevation, freezing
point depression, and osmotic pressure are the colligative
properties.
 These properties are used to determine the molecular
weights and to measure water activity. The properties
include:
A) Boiling Point Elevation
B) Freezing Point Depression
C) Osmotic Pressure
A) Boiling Point Elevation
 If a small amount of nonvolatile solute is dissolved in a volatile
solvent and the solution is very dilute to behave ideally, the lowered
vapor pressure can be calculated from equation.
 Boiling point elevation (T – T0) can be expressed as ∆TB. When
boiling point elevation is not too large, the product of T times T0 can
be replaced by T02 .
 Considering the mole fraction of solute as XB, the mole fraction of
solvent is XA = 1 − XB
 ln (1 – XB) can be expanded in a power series as:

 For dilute solutions where XB is a very small fraction, the equation


can be written as:

Where 

In which wB and wA are the masses of solute and solvent, respectively


and MB and MA are the molecular weights of the solute and solvent,
respectively.
 Therefore,

Where ∆TB is boiling point elevation (T-T0), lv is the latent heat


of vaporization per unit mass

 The term (wB/wAMB) is expressed in terms of molality as


(m/1000). Then:

where KB is the molal boiling point elevation constant.


 This equation is valid for all non-electrolytes in which equal
numbers of moles are involved before and after the solution is
formed. For electrolytes, the equation can be expressed as:

where the i factor is the ratio of number of total moles after the
solution to the number of moles before the solution. For non-
electrolytes i = 1.

 To predict boiling point rise due to the solutes in the solution,


an empirical rule known as Dühring’s rule can be used. In this
rule, a straight line is obtained if the boiling point of solution is
plotted against the boiling point of pure water at the same
pressure for a given concentration. For each concentration and
pressure a different line is obtained.
Exercise 1
(a) Determine the boiling temperature of 10% (w/w) NaCl solution
under atmospheric pressure.
Check the result also from the Dühring plot.
(b) By using the Dühring plot, estimate the boiling point of the
same solution under a pressure of 47.39 kPa. What is the boiling
point elevation at this pressure if at 47.39 kPa water boils at
80◦C?
Data: Molecular weight of NaCl: 58.4 g/g-mole
Enthalpy of saturated vapor: 2676.1 kJ/kg at 100◦C
Enthalpy of saturated liquid: 419.04 kJ/kg at 100◦C
R, gas constant: 8.31434 kJ/kg-mole K.
Dühring chart for aqueous solutions of NaCl
Solution

(a) For electrolytes such as NaCl, KB can be calculated using

Molality is the number of moles of solute in 1000 g of


solvent. Molality of 10% sodium chloride solution can be
calculated by using its molecular weight:
The i factor for NaCl is 2. Then,
△TB = i KBm = (0.513)(1.9)(2) = 1.95◦C
TB = 100 + 1.95 = 101.95◦C

From Dühring chart, the boiling point of the solution


is read as 103◦C

(b) At 47.39 kPa water boils at 80◦C. From the Dühring plot, the
boiling point of 10% NaCl solution for the pressure yielding boiling
point of water at 80◦C can be read as 83◦C. Therefore, the
boiling point elevation is:
∆TB = 3◦C
(B) Freezing Point Depression
When equilibrium exists between solid A and its solution,
the chemical potentials of A must be the same in both
phases:
μ S A = μ LA
For small freezing point depression:

where ∆T f is the freezing point depression.

Then, the equation can be written as:

where
 In freezing point depression, the term (wB/wAMB) is
expressed in terms of molality as (m/1000).
Then equation becomes:

where Kf is the molal freezing point depression constant.

 Freezing point depression is useful for determining the


molar mass of the solutes. These relations apply to ideal
solutions. For electrolytes,

where i is the ratio of number of total moles after the solution to


the number of moles before the solution. For non-electrolytes i =
1.
Exercise 2
In a city, the administrative board of the municipality is
discussing using salt (NaCl) or glycerol (C3H8O3) for road
treatment to eliminate ice. Assuming that you are one of the
engineers
taking part in the discussion, help them to decide which is the
more effective type of antifreeze.
Compare the performances of both types of solutions at the
same concentration such as 10% (w/w).

Data: Latent heat of fusion for ice at 0◦C: 6028.5 kJ/kg-mole


Molecular weight of glycerol: 92 kg/kg-mole
Molecular weight of water: 18 kg/kg-mole
The gas constant, R: 8.3143 kJ/kg-mole·K
Solution

Freezing point depression is calculated as

For NaCl solution, molality of 10% sodium chloride solution is 1.9


m,
The i factor for NaCl solution is 2. Then, freezing point depression
is:
∆Tf,NaCl = (1.85)(1.9)(2) = 7.03◦C
For a 10% glycerol solution molality is calculated as:

The i factor for glycerol is 1.


∆Tf,gly = (1.85)(1.21)(1) = 2.24◦C

Since ∆Tf,NaCl is greater than ∆Tf,gly for the same concentration,


NaCl is a more effective antifreeze.
C) Osmotic Pressure
 Osmotic pressure is a colligative property that is closely related
to the vapor pressure, freezing point, and boiling point.
 The activity of the solvent affects mostly osmotic pressure.
 An osmotic pressure arises when two solutions of different
concentrations are separated by a semipermeable membrane.
 Figure below shows the osmometer showing conditions at
equilibrium.
 The solution and solvent are separated by a semipermeable
membrane that allows only passage of solvent. Osmotic flow
continues until the chemical potential of the diffusing
component is the same on both sides of the barrier.
 The equilibrium occurs in an osmometer in which the extra
pressure π necessary for equilibrium is produced by the
hydrostatic pressure of a water column on the solution side.
 At equilibrium there will be no net flow of solvent across the
membrane so the chemical potential of pure solvent at
pressure P must be equal to the chemical potential of
solvent in solution at pressure P + π.

μA(solution, P + π) = μA(solvent, P)

 At constant temperature and at 1 atm pressure:


μA(solution, 1 + π) = μ0A(solvent)
 The chemical potential of A at 1 atm is decreased owing to
the presence of solute in solution and it can be calculated as:
μosmosis = μA(solution, 1) − μ0A(solvent)

 After derivation from related equations:

where π is osmotic pressure (Pa), V is the volume of solution (m3), and


nB is the number of moles of solute in solution.
 In dilute solutions nA VA0 is equal to the volume of solution since the
volume of the solute is negligible.
Therefore:
πV = nBRT
⇒ π = cRT

where R is the gas constant (8314.34 m3· Pa/kg-mole·K) and c is the


concentration of solute (kg-mole/m3).