SOLUTIONS

Lecture 2
Solutions
• solution is a homogeneous mixture of two or more
substances on molecular level

• Solute – constituent of the solution that is present in

smaller amount

• Solvent - constituent of the solution that is present in

larger amount
Concentration of a Solution
• Concentration – amount of solute present in a given
amount of solution

• Dilute solution – is a solution which contains a relatively

low concentration of solute

• Concentrated solution – is a solution which contains

high concentration of solute
Expressing Concentration
• Percent by weight
• Mole fraction
• Molarity
• Molality
• Normality
Thermodynamic Description of Mixtures
• Partial molar volume
• Consider a binary mixture of a and b, it follows that the volume of
one component can be written as

𝜕𝑉
𝑉𝑎 =
𝜕𝑛𝑎 𝑝, 𝑇, 𝑛𝑏
Where:
Va = partial molar volume
V = total volume
na = moles of component a
Thermodynamic Description of Mixtures
• Partial molar volume

𝜕𝑉 𝜕𝑉
𝑑𝑉 = 𝑑𝑛𝑎 + 𝑑𝑛𝑏
𝜕𝑛𝑎 𝑃,𝑇,𝑛𝑏
𝜕𝑛𝑏 𝑃,𝑇,𝑛𝑎

Where:
V = total volume of the mixture
Examples:
• At 25°C, the density of a 50 percent by mass
ethanol/water solution is 0.914 g/cm3. Given that the
partial molar volume of water in the solution is 17.4 cm3
/mol, what is the partial molar volume of the ethanol?
Examples
• A polynomial fit to measurements of the total volume of a
water/ethanol mixture at 25°C that contains 1.000 kg of
water is

𝑉 = 1002.93 + 54.6664𝑥 − 0.36394𝑥 2 + 0.028256𝑥 3

Where V is the total volume in cm3, x is the amount of

ethanol in moles. Determine the volume of ethanol in the
solution if it contains 0.1 mol of ethanol.
Thermodynamic Description of Mixtures
• Partial molar Gibb’s
energies

𝜕𝐺
𝜇𝑎 =
𝜕𝑛𝑎 𝑝, 𝑇, 𝑛𝑏
Thermodynamic Description of Mixtures
• Fundamental equation of Chemical Thermodynamics

𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 + 𝜇𝑎 𝑑𝑛𝑎 + 𝜇𝑏 𝑑𝑛𝑏

• For a mixture under constant temperature and pressure,

𝐺 = 𝑛𝑎 𝜇 𝑎 + 𝑛 𝑏 𝜇 𝑏

𝑑𝐺 = 𝑊𝑛𝑒
Thermodynamic Description of Mixtures
• Derivation of Gibbs-Duhem Equation

𝑑𝐺 = 𝑑(𝑛𝑎 𝜇𝑎 ) + 𝑑(𝑛𝑏 𝜇𝑏 )
𝑑𝐺 = 𝜇𝑎 𝑑𝑛𝑎 + 𝑛𝑎 𝑑𝜇𝑎 + 𝜇𝑏 𝑑𝑛𝑏 + 𝑛𝑏 𝑑𝜇𝑏

At constant pressure and temperature,

𝒏𝒂 𝒅𝝁𝒂 + 𝒏𝒃 𝒅𝝁𝒃 = 𝟎

𝒊=𝒏

෍ 𝒏𝒊 𝒅𝝁𝒊 = 𝟎
𝒊=𝟏
Example
• The experimental values of the partial molar volume of
K2SO4(aq) at 298 K are found to fit the expression

1
𝑉𝐵 =
32.280 + 18.216𝑥 2
Where VB is the partial molar volume of K2SO4 in cm3/mol,
x is the molality of K2SO4

Use the Gibbs–Duhem equation to derive an equation for

the molar volume of water in the solution. The molar
volume of pure water at 298K is 18.079 cm3/mol.
Thermodynamics of Mixing
• Consider the system given below.
Before mixing component A has nA, T, PA1 nB, T, PB1
the parameters nA, T and p while
B has the parameters nB, T and p.
Combining the two gases will
yield a parameter defined by pA, nA, nB, PA2, PB2, T
pB and T.

• It follows that the Gibbs energy of the individual gases are

given by,
𝑃𝐴2
∆𝜇𝐴 = ∆𝐺𝐴 = 𝑅𝑇𝑙𝑛
𝑃𝐴1
𝑃𝐵2
∆𝜇𝐵 = ∆𝐺𝐵 = 𝑅𝑇𝑙𝑛
𝑃𝐵1
Thermodynamics of Mixing
Mixing the two gases will result to a Gibbs energy of,

𝑃𝐴2 𝑃𝐵2
∆𝐺𝑚𝑖𝑥 = 𝑛𝐴 𝑅𝑇𝑙𝑛 + 𝑛𝐵 𝑅𝑇𝑙𝑛
𝑃𝐴1 𝑃𝐵1
In cases at which the initial pressure of the gasses are equal
applying Dalton’s Law,

∆𝐺𝑚𝑖𝑥 = 𝑛𝑅𝑇[𝑥𝐴 𝑙𝑛 𝑥𝐴 + 𝑥𝐵 𝑙𝑛 𝑥𝐵 ]

Note that xA and xB are less than 1, it follows that

∆𝐺𝑚𝑖𝑥 < 0
Which means mixing of gases is an spontaneous process.
Examples
• A container is divided into two equal compartments. One
contains 3.0 mol H2(g) at 25°C; the other contains 1.0 mol
N2(g) at 25°C. Calculate the Gibbs energy of mixing when
the partition is removed. Assume perfect gas behavior.

• Suppose that 2.0 mol H2 at 2.0 atm and 25°C and 4.0 mol
N2 at 3.0 atm and 25°C are mixed at constant volume.
Calculate ∆mixG. What would be the value of ∆mixG had
the pressures been identical initially?
Other thermodynamic mixing function
• Entropy of Mixing

𝑑𝑃 𝑑𝐺
∆𝑆𝑚𝑖𝑥 =𝑉 −
𝑑𝑇 𝑑𝑇

• Special Case (Perfect gases initially at the same

pressure)
𝑑𝐺
∆𝑆𝑚𝑖𝑥 =−
𝑑𝑇
Other thermodynamic mixing function
• Enthalpy of Mixing

∆𝐺𝑚𝑖𝑥 = ∆𝐻𝑚𝑖𝑥 − 𝑇∆𝑆𝑚𝑖𝑥

• For isothermal and isobaric mixing,

∆𝐻𝑚𝑖𝑥 = 0
Chemical Potential of Solutions
• Concept of Ideal Solutions
• Consider a single-component system A

• For isothermal process,

Gas Phase
• Chemical potential of the liquid, A(g)

𝑃𝐴∗
𝜇𝐴(𝑙) − 𝜇 𝑟𝑒𝑓 = 𝑅𝑇𝑙𝑛
𝑃𝑟𝑒𝑓
Liquid Phase
• Chemical potential of the vapor, A(l)
𝑃𝐴
𝜇𝐴(𝑔) − 𝜇 𝑟𝑒𝑓 = 𝑅𝑇𝑙𝑛
𝑃𝑟𝑒𝑓
Chemical Potential of Solutions
• Concept of Ideal Solutions
• Eliminating the reference potential,

∗
𝑃𝐴
𝜇𝐴 𝑙 ,𝑝 = 𝜇𝐴(𝑔) + 𝑅𝑇𝑙𝑛 Gas Phase
𝑃𝐴
A(g)

• This equation represents the chemical potential of the

liquid and vapor at any instant.
Liquid Phase
A(l)
Where:
A(l),p is the chemical potential of the pure liquid
A(g) is the chemical potential of the vapor
PA* is the vapor pressure of the liquid
PA is the pressure of the vapor
Chemical Potential of Solutions
• Concept of Ideal Solutions
• If solute B is added to the component A, the latter can no longer
exert its total vapor pressure. Only a part is being exerted denoted
by pA.

𝑝𝐴
𝜇𝐴 𝑙 ,𝑚 = 𝜇𝐴 𝑙 ,𝑝 + 𝑅𝑇𝑙𝑛
𝑃𝐴∗
Gas Phase
A(g), B(g)
Recall Raoult’s Law (Francois Raoult),

𝑝𝐴 = 𝑥𝐴 𝑃𝐴∗
Liquid Phase
where: A(l), B(l)
xA is the mole fraction of A in the mixture
Chemical Potential of Solutions
• Concept of Ideal Solutions

• Ideal Solution
• A solution which obeys Raoult’s Law throughout the composition
range (xA = 0 to xA = 1)
• Average energy of interaction between A–B is the same with the
average energy of A–A and B–B interactions.

• Thus, the chemical potential of component A in an ideal

solution is given by

𝜇𝐴 𝑙 ,𝑚 = 𝜇𝐴 𝑙 ,𝑝 + 𝑅𝑇𝑙𝑛 𝑥𝐴
Chemical Potential of Solutions
• Concept of Ideal-Dilute Solution

• Partial pressure of the solute B

deviates significantly from the Raoult’s
Law as shown in the figure. Thus, the
derived chemical potential of solvent A
cannot be used to denote the chemical
potential of solute B.
Chemical Potential of Solutions
• Concept of Ideal-Dilute Solutions

• For dilute concentration of solute, relationship between the partial

pressure with that of concentration is given by Henry’s Law after
William Henry. It is given by,

𝑝𝐵 = 𝐻𝑝 𝑥𝐵
In terms of vapor composition,
𝑦𝐵 = 𝐻𝑐 𝑥𝐵

Where:
Hp = Henry’s Constant, unit of pressure
HC = Henry’s Constant, unit of concentration
yB = concentration of B in the vapor
xB = concentration of B in the liquid
pB = partial pressure of B in the vapor
Chemical Potential of Solutions
• Concept of Ideal-Dilute Solutions

• Thus, the chemical potential of solute B in an ideal

solution is given by

𝐻𝑝 𝑥𝐵
𝜇𝐵 𝑙 ,𝑚 = 𝜇𝐵 𝑙 ,𝑝 + 𝑅𝑇𝑙𝑛
𝑃𝐵∗
Properties of Solutions
• Liquid-liquid Mixtures

• For ideal liquid-liquid solutions, the ideal Gibb’s energy of

mixing under isothermal condition is

∆𝐺𝑚𝑖𝑥 = 𝑛 𝑇 𝑅𝑇[𝑥𝐴 ln 𝑥𝐴 + 𝑥𝐵 ln 𝑥𝐵 ]

Where:
nT = total number of moles = nA + nB
Properties of Solutions
• Liquid-liquid Mixtures

• For ideal liquid-liquid solutions, the ideal Entropy change of

mixing under isothermal condition is

∆𝑆𝑚𝑖𝑥 = −𝑛 𝑇 𝑅[𝑥𝐴 ln 𝑥𝐴 + 𝑥𝐵 ln 𝑥𝐵 ]

• Ideal Enthalpy change of mixing for isothermal and isobaric

process,

∆𝐻𝑚𝑖𝑥 = 0
• Ideal volume change of mixing for isothermal and isobaric
process,
∆𝑉𝑚𝑖𝑥 = 0
Properties of Solution
• Real liquid-liquid solution
• Real solution properties are the actual (true) values of the
properties of a solution mixture.

• Properties of Real solutions can be expressed interms of

excess function,

∆𝑃𝑟𝑜𝑝𝑒𝑟𝑡𝑦𝒓𝒆𝒂𝒍 = ∆𝑃𝑟𝑜𝑝𝑒𝑟𝑡𝑦𝒊𝒅𝒆𝒂𝒍 + 𝑃𝑟𝑜𝑝𝑒𝑟𝑡𝑦𝒆𝒙𝒄𝒆𝒔𝒔

Properties of Solution
• Real liquid-liquid solution

• A useful model in developing real solution properties is

the regular solution.

• Regular Solution
• Solution in which the excess enthalpy is not equal to zero but the
excess entropy is equal to zero.
• In notation form,
𝐻𝑒𝑥𝑐𝑒𝑠𝑠 ≠ 0; 𝑆𝑒𝑥𝑐𝑒𝑠𝑠 = 0
Properties of Solution
• Regular Solution

• Excess enthalpy of regular

solutions can be expressed
in terms of
𝐻𝑒𝑥𝑐𝑒𝑠𝑠 = 𝑛 𝑇 𝛽𝑅𝑇𝑥𝐴 𝑥𝐵

Where:
n = total number of moles
 = dimensionless parameter
If  < 0, mixing is exothermic Experimental excess Enthalpy of mixing of
If  > 0, mixing is endothermic benzene/cyclohexane at 25 0C
Properties of Solution
• Regular Solution

• Regular solution Gibb’s energy of mixing,

∆𝐺𝑚𝑖𝑥, 𝑟𝑒𝑔 = 𝑛 𝑇 𝑅𝑇[𝑥𝐴 ln 𝑥𝐴 + 𝑥𝐵 ln 𝑥𝐵 + 𝛽𝑥𝐴 𝑥𝐵 ]

Properties of Solution
Interpretation

For  > 2, two-phases will form with a

corresponding concentration given by the two
minimum points.

Gibb’s energy of mixing for different values of

the parameter β
Colligative Properties
• For dilute solutions, properties which depends on the
number of solute particles present and not on the
nature of those particles is called Colligative Properties.

• Common Colligative Properties

• Boiling point rise
• Freezing point depression
• Osmotic pressure
Colligative Properties
• For dilute solutions, properties which depends on the
number of solute particles present and not on the
nature of those particles is called Colligative Properties.

• Common Colligative Properties

• Boiling point rise
• Freezing point depression
• Osmotic pressure
Colligative Properties
• Concept of Boiling Point
Elevation and Freezing Point
Depression

𝜇𝐴 𝑙 ,𝑚 = 𝜇𝐴 𝑙 ,𝑝 + 𝑅𝑇𝑙𝑛 𝑥𝐴
Colligative Properties
• Boiling Point Rise Compound Kf Kb
(K/molal) (K/molal)
Water 1.86 0.512
∆𝑇 = 𝐾𝑏 𝑚
Benzene 5.12 2.53
Where: Acetic Acid 3.90 3.07
T = Boiling Point Rise Nitrobenzene 7.00 5.24
Kb = boiling-point constant
Phenol 7.40 3.56
m = molalilty
Camphor 40.0 5.61
• Freezing Point Depression

∆𝑇 = 𝐾𝑓 𝑚

Where:
Kf = freezing point constant
Colligative Properties
• Osmosis
• the spontaneous passage of a pure solvent into a solution
separated from it by a semipermeable membrane, a membrane
permeable to the solvent but not to the solute.

• Osmotic Pressure, 
the pressure that must be applied to the
solution to stop the influx of solvent.

 = 𝑀𝑅𝑇

Where:
M = molarity
R = universal gas constant
T = temperature