Ch5: Simple mixtures

The thermodynamic properties of

mixtures
For a binary mixture of A and B: . If there are more than 2
components (n components in the mixture): 
Partial molar quantities
Partial molar volume: The partial molar volume of a substance A in a
mixture is the change in volume per mole of A added to a large
volume of the mixture. Partial molar volume of the components of a
mixture vary with the composition because the environment of each
type of molecules changes as the composition changes. For example
if 1 mole of water is added to a huge volume of water the total
volume changes by ~18 ml (molar volume of water) but if the same
amount of water is added to a huge volume of ethanol the total
volume increases by only 14 ml
Partial molar volume
Partial molar volume of component J
is the variation in total volume at
constant P,T and number of moles of
all other component except for J. In
other words, partial molar volume of
J is the slope of the plot of the total
volume versus the number of moles
of component J
Partial molar volume


VA(a)

VA(b) Molar volumes are always

positive, but partial molar
volume can be either
positive or negative
 For a binary mixture of A and B, and
. At constant P and T, volume only depends on nA and nB so  and 
 Experimental measurements show that in a given range of
composition, the total volume of a solution of water-ethanol that
contains 1.000 kg of water can be expressed in terms of the mole
fraction of ethanol via the following equation where nE is the
number of moles of ethanol. What is the partial molar volume of
ethanol?

Partial molar quantities
Partial molar Gibbs energy OR CHEMICAL POTENTIAL in a solution is
defined as the derivative of Gibbs energy with respect to the number
of moles. Remember that for pure substances we had (chemical
potential is molar Gibbs energy)
Similar to volume, we can write:
We can extend the exact differential:


At constant P and T, we have: 
We can show that chemical potential can be in fact written as



Gibbs-Duhem equation
At constant P and T, 
In a mixture, chemical potential of one component cannot change
independently of the chemical potential of other components. In fact
we can show that  (Gibbs-Duhem)
In a binary mixture, 
The same line of reasoning applies to all partial molar quantities.
Thermodynamics of mixing
Recall from Chapter 4, for a pure substance:  so  or  So for a pure
substance . For a perfect gas where ,  so to compare the chemical
potential at any pressure with chemical potential at normal standard
pressure (standard chemical potential)  for a perfect gas
Consider two perfect gases A
and B
= +

𝑖
𝐴
𝐴
𝐵
𝐵
𝐺
𝑛
𝜇
𝑛
𝜇

 Consider two perfect gases A
and B






) <0
) <0
(a)A container with 2 compartments contains 3.0 mol of H2 in one
side and 1.0 mol of N2 in the other side at 25°C. The compartments
have equal pressures. Calculate the Gibbs energy of mixing when the
partition is removed.
(b) Consider the container in part a. what would be the Gibbs energy
of mixing if the compartments have equal volumes?
 Recall from Chapter 3 and 4: . So . We
can say that . Since
),
.
Note that for mixing of two or more perfect
gases,  > 0
 . So 
The enthalpy of mixing of two (or more) perfect gases is zero!
The chemical potentials of liquids
Ideal solutions: In this part pure substance properties are denoted with *.  is
the chemical potential of a pure substance and  is the chemical potential of
pure substance when in liquid state.
 chemical potential of pure substance a in liquid at equilibrium with its vapor.
If substance A is in a mixture with vapor pressure of PA then,
 so 
Raoult’s law:  for ideal solutions
 chemical potentials for components in an ideal solution (Both solvent and the
solute)
 ∗

𝐵
𝑃
Note that as , 
And as ,  ∗

𝐴
𝑃
The vapor pressures of pure substance A and B are 75 mmHg and
21 mmHg, respectively, What is the vapor pressure of a solution of
equi-molar mixture of A and B?
Many real solutions do not obey Raoult’s law. In
fact, in many real solutions at low concentrations,
the vapor pressure of the solute is proportional to
its mole fraction but the constant of proportionality
is not . KB (with unit of pressure) is chosen as the
constant of proportionality  (Henry’s law)
Henry’s law is a limiting law (as)
Ideal-dilute solutions: Mixtures in which solvent
obeys Raoult's law and the solute obeys Henry's
law.
 Solution of O2 in water obeys Henry’s law at low concentrations.
What would be O2 molality (mol of solute in 1 kg of solvent ) in water
if its partial pressure is 21 kPa (K=7.9×104 kPakg/mol)

Chapter 5A
Properties of solution
Reminder: for ideal solutions,
,
Similar to perfect gases, we can show that:
),  < 0
,  > 0
. Since , for ideal solutions, 
Colligative properties
Properties that depends on the amount of solute (number of solute
particles present) and not on the identity of the solute.
Colligative properties are: lowering of vapor pressure,
elevation of boiling point, depression of freezing
point, and the osmotic pressure.
From this point on A: solvent, B: solute
Assumptions in studying the colligative properties: 1. solutions are
ideal. 2. solute is NOT volatile so it DOES NOT contribute to the
vapor pressure. 3. solute DOES NOT dissolve in solid solvent so when
the solution is frozen, only PURE solid solvent separates.
Vapor pressure depression: 

 vapor
∗
()= ( , )

𝐴
𝐴
𝜇
𝑙
𝜇
𝑔
𝑝
Equal at
equilibrium

 liquid

(a) Pure liquid, highly ordered (b) In the presence of solute (yellow squares) the disorder in the liquid
phase is higher than that of the pure liquid phase and the tendency to acquire the disorder
characteristics of the vapor decreases.
Show that for an ideal mixture of A and B, vapor pressure of mixture
changes by 
 The chemical potential of solvent is reduced in the presence of
solute:
.
 The chemical potential of solvent is reduced in the presence of
solute:
.
 The elevation of boiling point: 
: change in boiling point
: van’t Hoff factor, how many particles are produced by 1 particle of
solute: for NaCl: =2 for MgCl2 =3 for sugar =1
: empirical boiling point constant of the solvent
: molality: number of moles of solute in 1kg of solvent

Lower tendency of solvent to form vapor results in elevation of

boiling point. Purely entropic!
The boiling point constant of water is 0.51 Kkg/mol. Calculate boiling
point of water in a solution of 0.010 mol/kg of sugar and a solution
of 0.010 mol/kg of NaCl
 Which of the following aqueous solutions has higher boiling point?
0.010 m KCl 0.010 MgCl2
0.010 m KCl 0.020 NaCl

Which of the following solutions has higher boiling point?

0.10 m aqueous solution of A or 0.10 m of the same solute in Benzene?
(water: Kb=0.51 Kkg/mol, Benzene: Kb=2.53 Kkg/mol)
The depression of freezing point: The elevation of entropy of the
solution opposes the tendency to freeze.

∗
()= ( )

𝐴
𝐴
𝜇
𝑙
𝜇
𝑠
 The depression of freezing point: 
: change in freezing point
: van’t Hoff factor, how many particles are produced by 1 particle of
solute: for NaCl: =2 for MgCl2 =3 for sugar =1
: empirical freezing point constant of the solvent
: molality: number of moles of solute in 1kg of solvent
 Freezing point constant of water is 1.86 Kkg/mol and for an unknown
solvent is 40 Kkg/mol. Calculate freezing point depression for 0.10 m
solution of sugar in each of these solvents.

Calculate freezing point depression for 0.010 m solution of NaCl in

each of these solutions.

Chapter 5B.1(a), 5B.2(a-c)

Non-ideal solutions with positive or negative deviation
Intermolecular
interactions between
solvent and solute are as
strong as those between
solvent and solute KA

KB

 (ideal solutions)
V =0
 =0
Non-ideal solutions with positive or negative deviation
Non-ideal solutions with positive or negative deviation
Non-ideal solutions with positive or negative deviation
Intermolecular Intermolecular Intermolecular
interactions between interactions between interactions between
solvent and solute are as solvent and solute are solvent and solute are
strong as those between weaker than those stronger than those
solvent and solute KA between pure solvent between pure solvent
and pure solute and pure solute

KB

KA

KB

 (ideal solutions)  (ideal solutions)  (ideal solutions)

V =0 V >0 V <0
 =0  >0  <0
 Which of the following have largest deviation from ideality?

0.10 M solution of glucose or 0.10 M solution of NaCl

0.10 M solution of KCl or 0.10 M of MgCl2
The vapor pressures of pure substance A and B are 75 mmHg and
21 mmHg, respectively, What is the vapor pressure of a solution of
equi-molar mixture of A and B? What is the composition of the
vapor?
Phase diagrams of binary systems
Vapor pressure diagram:
For ideal solutions:  and  so
 or 
 If and  are mole fractions of A and B in vapor,
 and  so  and 
We can show that 
Curves are
labeled with the
value of 
How to interpret the Diagram?

a depicts the composition of the

solution (liquid) or mole fraction of
A in solution. b is the composition
of the vapor at equilibrium with the
liquid or mole fraction of A in the
vapor
Temperature composition diagrams
For an ideal mixture with A more
volatile than B:
gas Fractional distillation for ideal solutions:
Liquid with composition a1 is warmed up to T2
and starts to boil. The liquid at this temperature
has composition a2 (the same as a1). The trace of
vapor at this temperature has composition of a2’.
If we collect the vapor with a2’ composition and
cool it down, once it riches T3, it condensates and
the composition of the new liquid is a3 which is at
equilibrium with trace of vapor with a’3 which,
gas + liquid once condensed, results a liquid with a4
composition. By repeating this process we can
obtain a liquid which is almost purely A.

liquid
 negative Azeotrope
Positive Azeotrope (high boiling
(low boiling azeotrope)
Azeotropes: azeotrope)
Positive deviation of
negative deviation of
mixture of two Raoult’s law
Raoult’s law
liquids that has a gas
constant boiling gas
point and gas + liquid
composition Azeotrop
throughout e
distillation gas + g
liquid
Not all non-ideal a
s
solutions will form gas + Azeotrop
azeotropes! liquid e
+

l
liquid i
liquid q
u
i
Chapters 5C.1 (a,b) 5C.2(a,b) d
Next part: 5.E
Activity
For solvent:
Remember:  according to the Raoult’s law:
. So for ideal solutions, .
Extension to real solutions:  and 
as 
We can also write: ( activity coefficient) so as 


Standard state of solvent: 1 bar and =1

What is the activity of a solvent if its vapor pressure is lowered from
45.0 torr(pure solvent) to 25.0 torr when 2 moles of solute is
dissolved in 4 moles of solvent. What is the solvent activity
coefficient?

Is this solution ideal? What kind of deviation does it have?

 For solute:
Note that the solutions approach ideal-dilute behavior as xB→0 and
not 1!
For ideal-dilute solutions,  so

If the solution is ideal,  and 
 Real solutions:
 and  and . Note that for solutes:
 and  as 
 Use the following data to calculate activity coefficient of CHCl3(C) in
acetone (A) treating it first as a solvent and then as a solute
(Henry’s constant for C in A solution is 22.0 kPa)

See the following: http://www4.ncsu.edu/~franzen/public_html/CH331/assign/Activity_coeff.pdf

Use the following data to calculate activity coefficient of CHCl3(C) in
acetone (A) treating it first as a solvent and then as a solute (Henry’s
constant for C in A solution is 22.0 kPa)

If treated as a solvent, we use Raoult’s law to calculate the activities.

From the data, =36.4 kPa
Use the following data to calculate activity coefficient of CHCl3(C) in
acetone (A) treating it first as a solvent and then as a solute (Henry’s
constant for C in A solution is 22.0 kPa)

If treated as a solute, we use Henry’s law to calculate the activities. K=22.0 kPa
Use the following data to calculate activity coefficient of CHCl3(C) in
acetone (A) treating it first as a solvent and then as a solute (Henry’s
constant for C in A solution is 22.0 kPa)

If treated as a solute, we use Henry’s law to calculate the activities. K=22.0 kPa
 Use the following data to calculate activity coefficient of CHCl3(C) in
acetone (A) treating it first as a solvent and then as a solute
(Henry’s constant for C in A solution is 22.0 kPa)

See the following: http://www4.ncsu.edu/~franzen/public_html/CH331/assign/Activity_coeff.pdf

 Activities can be written in terms of molalities
 (standard molality is 1 mol/kg)
Just like before, if we define  and  as 
Then 

Chapter 5E
Activity of ions
For an electrolyte such as MX (M+, X-), molar Gibbs energy of the ions
in electrically neutral solution is:

Activity of ions
For an electrolyte such as MX (M+, X-), molar Gibbs energy of the ions in
electrically neutral solution is:
 and for each ion (J) we can write:
. For a real solution:

We define:  (mean activity coefficient) so

For MpXq : 
Debye Huckel limiting law:
The long range Coulombic interactions between ions are the main
cause of deviation from ideality in ionic solutions.
(blue + gray -)
Anions are more likely to be found around cations and vise versa
Time averaged spherical haze around the central ion has a net
charge equal in magnitude but opposite in sign to that on the
central ion and is called atomic atmosphere
The chemical potential of the central ion is lowered as a results of
its electrostatic interaction with its atomic atmosphere
Based on this model, at very low concentration:
, A=0.509 for water at 25°C, z: charge, I (ionic strength)

, A=0.509 for water at 25°C, z: charge, I (ionic strength) 
What is the mean activity coefficient for 0.0050 mol/kg solution of
KCl? (answer: 0.9204)
What is the mean activity coefficient for 0.0050 mol/kg solution of
CaCl2? (answer: 0.7504)
Which one would have larger deviation from Debye-Huckel? 0.050
mol/kg solution of MgCl2 or 0.050 mol/kg solution of NaCl?

Which one would have larger deviation from Debye-Huckel? 0.050

mol/kg solution of CaCl2 or 0.010 mol/kg solution of CaCl2?