BKF1253 Physical Chemistry

Chapter 4: The Properties of Mixture

Prof. Madya Dr. Syed Mohd Saufi

Dr SMS
Topic
• The thermodynamic description of mixtures
– Measures of concentration
– Partial molar properties
– Ideal solutions
– Ideal-dilute solutions
• Colligative properties
– Modification of boiling and freezing points
– Osmosis
What Expected to Learn
https://www.youtube.com/watch?v=hOhgXRukRDg&t=2s

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Measurement of Concentration

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Solute vs Solvent vs Solution
• Solution - homogenous mixture of 2 or more substances.
• Solute - substance(s) present in the smaller amount(s) in the solution
• Solvent - substance present in the larger amount in the solution
Concentration Measurement
• Concentration is a quantitative study of a solution.

Molarity (M) Molality (m) Mol Fraction (xj)

• Molarity = mol of solute • Molality = mol of solute • Mole fraction (xj) =
• (mol)
Molarity/ volume of solute
= mol of • (mol) / mass
Molality = mol ofof
solvent
solute moles of component J /
solution (L or dm
(mol) / volume of
3
) (kg)
(mol) / mass-1 of solvent total moles of
• Unit mol(Ldm
solution
-3
(M)3)or
or dm • Unit
(kg) mol kg (m) component
• mol
Unit Lmol dm-3 (M) or
-1
•• Molality
Unit mol not
kg-1 affects
(m) by
• Molar
mol L-1concentration • temperature
Molality not affects by
• varies
Molar with temperature
concentration temperature
-varies
whenwith
temperature
temperature
increase, the solution
- when temperature
expand
increase,and
thecontract.
solution
expand and contract.

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Exercise
Calculate the molality of a sulfuric acid containing 24.4 g of sulfuric acid in
198 g of water. The MW of sulfuric acid is 98.08 g/mol.
Ans: 1.256 m
Exercise
What is the molality of a 5.86 M ethanol (C2H5OH) solution whose density is
0.927 g/mL?
Ans: 8.919 m
Exercise
Determine the mole fraction of glycine molecules in 0.14 m NH2CH2COOH
(aq).
Ans: Xgly = 2.514.x 10-3
Phase Stability for Pure Substance

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The Condition of Stability
• The
  molar Gibbs energy, - an intensive property, depends on the phase of
the substance.
• Gm of liquid water is different from water vapour at the same temperature
and pressure
• A substance has a spontaneous tendency to change into the phase with
the lowest molar Gibbs energy.
• At certain temperature and pressure, if the solid phase of a substance has
lower molar Gibbs energy than its liquid phase, then the solid phase is
thermodynamically more stable and liquid freeze.
• If the opposite is true, the liquid phase is thermodynamically stable and
the solid will melt.
• For example, at 1 atm, ice has a lower molar Gibbs energy than liquid
water when the temperature is below 0°C, and under these con- ditions
water converts spontaneously into ice.
The Variation of Gibbs Energy with Pressure
•  The changes in molar Gibbs energy of a substance when the pressure is
varied at constant temperature is :

• Where is the molar volume of the substance

• Based on this equation we can say that:
– An increase in pressure , results in an increase in molar Gibbs energy (
– For a given change in pressure, the resulting change in molar Gibbs energy is
greatest for substances with large molar volumes.
• Because the molar volume of a gas is much larger than that of a
condensed phase (a liquid or a solid), the dependence of on is much
greater for a gas than for a condensed phase.
• For most substances (water is an important exception), the molar volume
of the liquid phase is greater than that of the solid phase. Therefore, for
most substances, the slope of a graph of against is greater for a liquid
than for a solid.
The Variation of Gibbs Energy with Pressure

• At low pressure the gas phase is the most stable, then at sufficiently higher
pressures the liquid phase becomes the most stable, followed by the solid phase.
The Variation of Gibbs Energy with Pressure
• For
  solid and liquid, the molar volume is almost independent of pressure
• With , and

)
)

• This equation shows that the molar Gibbs energy of a solid or liquid
increases linearly with pressure.
• However, because the molar volume of a condensed phase is so small, the
dependence is very weak, and for the typical ranges of pressure normally
of interest to us we can ignore the pressure dependence of G

Dr SMS
The Variation of Gibbs Energy with Pressure
• The
  molar Gibbs energy of a gas, depend on the pressure, and because
the molar volume of a gas is large, the dependence is significant.

• This equation shows that the molar Gibbs energy increases logarithmically
(as ln p) with the pressure

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The Variation of Gibbs Energy with Temperature
• The
  change in molar Gibbs energy at constant pressure for small changes
in temperature is

• Because molar entropy is +ve, an increase in temperature (ΔT>0) results in

decrease in molar Gibbs energy, (
• The change in molar Gibbs energy is proportional to the molar entropy, so
the greater the molar entropy, the stronger the response of the molar
Gibbs energy to a change in temperature

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The Variation of Gibbs Energy with Temperature
• Gas phase is more spatial disorder
than in condensed phase, so the
molar entropy of the gas phase is
greater than that for a condensed
phase.
• The molar Gibbs energy falls more
steeply with temperature for a gas
than for a condensed phase
• At low temperature, the solid phase
has the lowest molar Gibbs energy
and is therefore the most stable.
• As the temperature is raised, the
molar Gibbs energy of the liquid
phase falls below that of the solid
phase and the substance melts.
• At even higher temperature, the
molar Gibbs energy of the gas phase
plunges down below that of the liquid
phase and the gas becomes the most
stable phase
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Partial Molar Properties

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Partial Molar Volume
•  A partial molar property is the contribution (per mole) that a substance
makes to an overall property of a mixture
• Example is partial molar volume of substance J, is the contribution of
substance J makes to the total molar volume of a mixture
• Although 1 mol of a substance has a characteristic volume when it is pure,
1 mol of that substance can make different contributions to the total
volume of a mixture because molecules pack together in different ways in
the pure substances and in mixtures.
• When 1 mole H2O is added to a huge volume of pure water, the volume
increase 18 cm3. The quantity 18 cm3/mol is the partial volume of water in
pure water.
• When 1 mol H2O is added to a huge volume of pure ethanol, the volume
increase 14 cm3. The quantity 14 cm3/mol is the partial volume of water in
pure ethanol.

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Partial Molar Volume

•  The partial molar volumes of the

component of a mixture vary with
composition because the
environment of each type
molecule changes as the
composition changes from pure A
to pure B.
• Once the partial molar volumes VA
and VB of a mixture are known,
total volume V of the mixture is:

Dr SMS
Partial Molar Volume - Exercise

What is the total volume of a mixture

of 50 g of ethanol and 50 g of water at
25oC?
Given Mwater = 18g/mol; Methanol =
46.07g/mol.

Ans = 110cm3

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Partial Molar Volume - Exercise
Calculate the mass density of a mixture of 20 g of water and 100 g of ethanol.

Ans = 0.835 g cm-3

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Partial Molar Volume - Exercise
•At 25C,
  the density of a 50% 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?

Ans = 56.215 cm3/mol

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Partial Molar Volume - Exercise
The partial molar volumes of propanone (MW = 58.08) and trichloromethane
(MW = 119.38) in a mixture in which the mole fraction of trichloromethane is
0.4693 are 74.166 cm3/mol and 80.235 cm3/mol, respectively. What is the
volume of a solution of total mass 1 kg.

Ans = 886.812 cm3

Dr SMS
The Chemical Potential
• Partial
  molar Gibbs energy, GJ of a substance J is the contribution of J (per
mole J) to the total Gibbs energy of a mixture.

• Partial molar Gibbs energy is so important in chemistry that it gives a

special name and symbol, chemical potential ()

• Chemical potential () is a measure of the ability of the substance to bring

about physical and chemical change.
• A substance with a high chemical potential has a high ability to drive a
reaction or some other physical process forward.

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Chemical Potential of Gas
• The
  chemical potential of perfect gas mixture is given by following
equation

• Where is standard chemical potential of the gas J and is standard

pressure (1 bar)
• The higher the partial pressure of the gas, the higher the chemical
potential.
• The higher the chemical potential, the more active chemically the species.
• If the partial pressure of perfect gas in a mixture changes from to , the
changes in its chemical potential is

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Spontaneous Mixing of Perfect Gases
• A
  system is at equilibrium when the chemical potential of each substance
has the same value in every phase in which it occurs
• The mixing of gas is spontaneous as the
• The total Gibbs energy when gases an amount of A and of B mixed at
constant temperature and pressure is given by:

• Because xA and xB are both less than 1, the two logarithms are negative (ln
x < 0 if x < 1), so ∆G < 0 at all compositions. Therefore, perfect gases mix
spontaneously in all proportions.

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Spontaneous Mixing of Perfect Gases
•  We can rearrange previous equation to get the enthalpy of mixing and
entropy of mixing

• There is no change in enthalpy when two perfect gases mix, which reflect
there is no interactions between molecules
• The entropy of mixing is given by:

• When two perfect gas mixed, the entropy increase because the mixed gas
is more disordered than the unmixed gas.

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Exercise
Consider two perfect gases A and B. Suppose 1 mol A is at 100 kPa and 298K
in one container and 1 mol B is in a neighboring container at the same T and
P. Calculate the changes in molar Gibbs energy, enthalpy and entropy when
these gases mix.

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Ideal Solution

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Raoult’s Law and Ideal Solutions
• Raoult’s
  law measure the partial pressure of the vapour of each component
in dynamic equilibrium with the liquid mixture

– The partial vapour pressure of a substance () in a liquid mixture is proportional to

its mole fraction ( in the mixture and its vapour pressure when pure ()

• In the pure solvent, the molecules are dispersed and have a corresponding
entropy; the vapour pressure then represents the tendency of the system
and its surroundings to reach a higher entropy.
• When solute is present, the solution has a greater disorder than the pure
solvent because a molecule chosen at random might be nt a solvent molecule
• Because of the entropy of solution is higher than that of the pure solvent, the
solution has a lower tendency to acquire an even higher entropy by the
solvent vaporizing
• Therefore, the vapour pressure of the solvent in the solution is lower than
that of pure solvent.

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Raoult’s Law and Ideal Solutions
• Ideal solution is hypothetical solution that obey Raoult’s Law at all compositions.
• The law is most reliable for actual solutions when have similar molecular shapes and are held
together in the liquid by similar types and strength of intermolecular forces. An example is
mixture of two similar hydrocarbon such as benzene-toluene mixture.
• No mixture is truly ideal and all real mixtures show deviations from Raoult’s law.
• Raoult’s Law is reliable for the solvent when the solution is very dilute.

Dr SMS
Exercise
•A solution
  is prepared by dissolving 1.5 mol naphthalene (MW = 128.17) in 1
kg of benzene (MW = 78.11). The vapour pressure of pure benzene is 12.6
kPa at 25C. What is the partial vapour pressure of benzene in solution?

Ans: 11.277 kPa

The Chemical Potential of Solvent
•  The chemical potential of a solvent A present in solution at a mole fraction
is

– where is the chemical potential of pure A.

– This expression is valid throughout the concentration range for either
component of a binary ideal solution.
• Because < 1 implies that ln < 0, the chemical potential of a solvent is
lower in a solution than when it is pure (when = 1).
• Provided the solution is almost ideal, a solvent in which a solute is present
has less chemical ‘punch’ (including a lower ability to generate a vapour
pressure) than when it is pure.
• The change in chemical potential of the solvent caused by a solute is given
by

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Spontaneous Mixing of Ideal Solution
•  ∆G should be negative if solute dissolve spontaneously to form an ideal
solution. The calculation is essentially the same as for the mixing of two
perfect gases.
• The total Gibbs energy of dissolving ideal solution is given by:

• The enthalpy of dissolving ideal solution is given by:

• The entropy of dissolving ideal solution is given by:

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Ideal - Dilute Solution

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Henry’s Law
• Raoult’s
  law provides a good description of the vapour pressure of the solvent
in a very dilute solution, when the solvent A is almost pure.
• However, we cannot in general expect it to be a good description of the
vapour pressure of the solute B because a solute in dilute solution is very far
from being pure.
• In a dilute solution, each solute molecule is surrounded by nearly pure
solvent, so its environment is quite unlike that in the pure solute and except
when solute and solvent are very similar (such as benzene and
methylbenzene)
• In dilute solutions, the vapour pressure of the solute is proportional to its
mole fraction times the Henry’s law constant,

• is is called Henry’s law constant (same unit as pressure) and is characteristic

of the solute.
• Solutions that are dilute enough for the solute to obey Henry’s law are called
ideal–dilute solutions.

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Henry’s Law
• Henry's
  law is commonly written to show the molar concentration of
dissolved gas depends on its partial pressure in the vapor phase above the
solvent

• Henry’s constant, , is commonly reported in mol kPa-1 m-3. This form of the
law and these units make it very easy to calculate the molar concentration
of the dissolved gas, simply by multiplying the partial pressure of the gas
(in kPa) by the appropriate constant.
• This equation can be used to estimate the concentration of O2 in natural
waters or the concentration of carbon dioxide in blood plasma.

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Exercise
The concentration of O2 in water required to support aerobic aquatic life is
about 4 mg dm-3. What is the minimum partial pressure of oxygen in the
atmosphere that can achieve this concentration? Given KH for oxygen is 1.30
x 10-2 mol/m3.kPa. (Hint: Convert mass concentration to mol concentration)

Answer: 9.615 kPa.

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Exercise
What partial pressure is needed to dissolve 21 mg of CO2 in 100 g of water at
25C? (MW CO2 = 44.01 g/mol)

Answer = 14.077 kPa

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Chemical Potential of the Solute
• Henry’s
  law is used to write an expression for the chemical potential of a
solute in a dilute solution.
• The chemical potential of the solute when it is present at a mole fraction
is

• It is often more natural to express the composition of a solution in terms

of the molar concentration of the solute, , rather than as a mole fraction.

• If the pressure is 1 bar, the eq. becoming

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Colligative Properties

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Colligative Properties
• The solute does affect the entropy by introducing a degree of disorder
that is not present in the pure solvent. We can therefore expect a solute to
modify the physical properties of the solution.
• Non-volatile solute has three main effects:
– Raise the boiling point of a solution
– Lower the freezing point
– Raise the osmotic pressure
• Colligative properties are properties that depend only on the number of
solute particles in solution and not on the nature/chemical identity of the
solute particles.
• Colligative denoting 'depending on the collection’
Modification of Boiling Points and Freezing Points

• The
  elevation of boiling point, and The depression of freezing point, are
proportional to the molality of the solute,
• The elevation of boiling point is given by

• The depression of freezing point is given by

– Where is is the ebullioscopic constant and is the cryoscopic constant of the solvent.
They are also called the ‘boiling-point constant’ and the ‘freezing-point constant’,
respectively.

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Depression of Freezing Points
• Assumptions:
– The solute is not volatile, and therefore does not appear in the vapour phase.
– The solute is insoluble in the solid solvent, and therefore does not appear in
the solid phase.
• The chemical potentials of pure solid
solvent and pure liquid solvent decrease
with temperature, and the point of
intersection, where the chemical
potential of the liquid rises above that of
the solid, marks the freezing point of the
pure solvent.
• A solute lowers the chemical potential of
the solvent but leaves that of the solid
unchanged. As a result, the intersection
point lies further to the left and the
freezing point is therefore lowered.

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Elevation of Boiling Points

• The chemical potentials of pure solvent

vapour and pure liquid solvent decrease
with temperature, and the point of
intersection, where the chemical
potential of the vapour falls below that of
the liquid, marks the boiling point of the
pure solvent.
• A solute lowers the chemical potential of
the solvent but leaves that of the vapour
unchanged.
• As a result, the intersection point lies
further to the right, and the boiling point
is therefore raised.

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Exercise
Estimate the freezing point depression of 100 cm3 of water sweetened with
3.0 g of sucrose.
(MW sucrose: 342.3 g mol-1; cryoscopic constant: 1.86 K kg mol-1)

Answer: 0.163 K

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Exercise
The addition of 5.00 g of a compound to 250 g of naphthalene lowered the freezing
point of the solvent by 0.780 K. Calculate the molar mass of the compound. (K f = 6.94
K kg/mol for naphthalene)

Ans: 177.95 g/mol

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Osmosis
• Osmosis is the selective passage of solvent molecules through a porous
membrane from a dilute solution to a more concentrated one.
• A semipermeable membrane allows the passage of solvent molecules but
blocks the passage of solute molecules.
• Osmotic pressure (π) is the pressure that must be applied to the solution
to stop the inward flow of the solvent.
Osmotic Pressure
• The osmotic pressure is directly proportional to concentration of solution
• The expression for the osmotic pressure of an ideal solution is given by the
van ’t Hoff equation
𝜋  V =𝑛 𝐵 𝑅𝑇

𝜋  =𝑐 𝐵 𝑅𝑇

• Osmosis helps biological cells maintain

their structure. Cell membranes are
semipermeable and allow water, small
molecules, and hydrated ions to pass,
while blocking the passage of
biopolymers synthesized inside the cell
• One of the most common applications of
osmosis is osmometry, the measurement
of molar masses of proteins and synthetic
polymers from the osmotic pressure of
their solutions
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Exercise
A solution is prepared by dissolving 35.0 g of hemoglobin (Hb) in enough
water to make up 1 L in volume. If the osmotic pressure of the solution is
found to be 10.0 mmHg at 25C, calculate the molar mass of hemoglobin.

Answer: 65 043.67 g/mol

Dr SMS