Topic 5 Solution

Reference: Atkins, 10th Edition, Chapter 5

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 Topics

 Ideal solutions
 Simple mixtures
 Partial molar volumes
 Surface Tension
 Capillary rise
 Adhesive force
 Equation of Young and Laplace
 Colligative properties

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 What is ideal solution?
When two substances whose molecules are
very similar form a liquid solution, the vapor
pressure of the mixture is very simply related
to the vapor pressures of the pure
substances.
An ideal solution or ideal mixture is a solution with thermodynamic properties
analogous to those of a mixture of ideal gases.

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Figure 1. Vapor-liquid equilibria for (a) pure toluene; (b) a mixture of equal
amounts of toluene and benzene: and (c) pure benzene. In the solution (b) only
half the molecules are benzene molecules, and so the concentration of benzene
molecules in the vapor phase is only half as great as above pure benzene. Note
also that although the initial amounts of benzene and toluene in the solution were
equal, more benzene than toluene escapes to the gas phase because of
benzene’s higher vapor pressure
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The partial vapor pressure of A above the liquid mixture, pA, will then be
the vapor pressure of pure A, PA*, multiplied by the fraction of the
molecules in the liquid which are of type A, that is, the mole fraction of A,
xA. In equation form

pA = xAPA*      (Raoult’s law) (1a)

Similarly for component B

pB = xBPB*      (1b)

Adding these two partial pressures, we obtain the total vapor pressure

P = pA + pB = xAPA* + xBPB*      (2)

Liquid solutions which conform to Eqs. (1) and (2) are said to obey
Raoult’s law and to be ideal mixtures or ideal solutions. 5
 Simple mixtures
 Chemistry – mixtures

 Mingled together

 They may react or not

The simplest is mixture of two unreacted substances, e.g. A and B

x A  xB  1

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 Partial molar volume

Adding 1 mole of water to a huge volume of pure water at STP. How

much volume increased? Volume increase is 18 cm3

Partial molar volume is 18 cm3/mol

Adding 1 mole of water to huge amount ethanol. Volume increase is 14 cm3

Partial molar volume is 14 cm3/mol

The volume change depend on the surrounding molecules.

Partial molar volume of ethanol in water is 14 cm3/mol

Partial molar volume of a substance A in a mixture is the change in volume

per mole of A added in large volume of the mixture.

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 For a mixture of A and B, partial molar
volume changes as the composition
change from pure A to pure B due to
change in molecular environment and
interaction forces between molecules.
This results in change of thermodynamic
properties

Partial molar volume of a substance , VJ

VJ

The subscript n’ signify the amount of other

Substances present are constant

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Thus VJ is the slope of plot of V vs n

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 The volume of the mixture changes with the addition of A and B. Take
infinitesimal amount, thus

dV = (eq. 1)

Thus for a constant composition of A and B with nA and nB being the

number of moles respectively

V= (eq. 2)

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 Measurement of partial molar volume
Measure the volume at different composition, plot the graph and fit to certain
function Example: Mixture of ethanol/water containing 1.000 kg of water

v  1002.93  54.6664 x  0.36394x 2  0.028256x 3 (Eq. 1)

Where v = total volume of mixture, V (cm3)
and x = nE (mol)

Figure 5.3 The partial molar

DIY: Calculate VE at 50% by mass of ethanol water volume of ethanol as expressed
by the polynomial in the brief
mixture with density 0.914 g cm-3. illustration. 11
VW = 17.4 cm3 mol-1. (Answer: 56.4 cm3 mol-1)
 Partial molar Gibbs energies
The same concept can be extended to extensive state function.

Chemical potential is defined as partial molar

Gibbs energy
 G  (eq 1)
 J   
 nJ  p ,T ,n '
For a pure substance we can write
G = nJGJ,m
from eq 1 obtain μJ = GJ,m

Thus for binary mixture

G  n A  A  nB  B

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Chemical potential, µ depend on composition, p and T. Thus Gibbs
energy changes when these variable changes. Thus for a system containing
A, B etc, fundamental equation of chemical thermodynamics

dG  Vdp  SdT   A dn A   B dnB  ...

For constant P and T,

dG   A dn A   B dnB  ... Eq. 5.7

Since dG  dwadd ,max thus

dwadd ,max   A dn A   B dnB  ...

Additional work can arise due to compositional change in a system!

Example: Electrochemical cell. Change in composition of electrolyte may
results in electrical work done by the cell.
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The chemical potential not only shows how G varies composition but can
also be proved to show how U, H and A change with composition

Internal Energy, U  U 
at constant  J   
vol, entropy and n’  nJ  S ,V ,n '

 H 
Enthalpy, H  J   
at constant  nJ  S , p ,n '
pressure, entropy and n’

 A 
Helmhotz energy, A 
J   
at constant
vol, temperature and n’
 nJ V ,T ,n '

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 Gibbs-Duhem equation

Since for binary system

G  n A  A  nB  B (eq 5.5)
Thus
dG   A dn A   B dnB  n A d A  nB d B
It has been shown that at constant p and T
dG   A dn A   B dnB (refer slide 13)

Which implies at constant T and P

n A d A  nB d B  0
Gibbs-Duhem eq.

 n d
J
J J 0
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Significant of Gibbs-Duhem eq.

Chemical potential of one component cannot be change independently of the

other component. If the partial molar quantity of one component increase the
other must decrease
nA
d B   d A
nB

Case for partial molar volume

nA
d B   d A
nB

DIY: study example 5.1 page 184 in Atkins and Paula, 2014

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Concentration

1) Molarity, c is the amount of solute divided by volume of the solution

(mol dm-3 or mol L-1). cƟ = 1 mol dm-3

2) Molality, b, is the amount of solute divided by the mass of solvents (mol kg-1)
bƟ = 1 mol kg-1
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Question!
The partial molar volumes of two liquids, A and B in a mixture in which
the mole fraction of A is 0.3713 are 188.2 cm3 mol−1 and 176.14 cm3
mol−1, respectively. The molar masses of A and B are 241.1 g mol−1
and 198.2 g mol−1.What is the volume of a solution of mass 1.000 kg?

Answer V = 843.5 cm3

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 Thermodynamic of mixing

Key points of thermodynamic mixing

i) The Gibbs energy of mixing calculated by forming the

difference of Gibbs energies before and after mixing: the
quantity is negative for perfect gases at the same pressure.

ii) The entropy of mixing of perfect gases initially at the same

pressure is positive and the enthalpy of mixing is zero

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 The Thermodynamic of Mixing; Gibbs Energy

 Mixing of ideal gas; ΔG = ?, ΔS = ?, ΔH = ?

Gi  n A  A  nB  B
 n A (  A  RT ln p )  nB (  B  RT ln p )

G f  n A  A  nB  B
 n A (  A  RT ln p A )  nB (  B  RT ln pB )

 mix G  G f  Gi
pA p
 n A RT ln  nB RT ln B
p p
 n A RT ln x A  nB RT ln xB

mole fraction; xA, xB < 1 ; thus; ΔmixG < 0

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  Example

3 mol H2(g) and 1.0 mol N2(g) at 25 oC are placed in 2 equal volume
containers. The gases were mixed by opening the valve between the
containers. Assume ideal gas behaviour, calculate ΔmixG.

pH 2 pN 2
 mix G  nH 2 RT ln  nN 2 RT ln
3p p
3
p 2 p
1
 3  RT ln 2
 1 RT ln  6.9 kJ
3p p

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 Homework!
2 mol H2 (g) at 2 atm and 25 oC and 4 mol N2 (g) at 3 atm and 25 oC are
mixed at constant volume. Calculate ∆mixG. What is the value of ∆mixG if the
pressure in the container are maintained constant? R=8.314 J·K−1·mol−1

Answer: [−9.7 kJ, −9.5 kJ]

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For a mixture of perfect gases initially at the same pressure, entropy of mixing

  mix G 
 mix S     nR( x A ln x A  xB ln xB )
 T  p ,n A ,nB

Since ln x < 0 thus ∆mixS > 0 for all composition

Entropy increase when gas is dispersed

mixH = 0

Can be proved
Because of no interactions between molecules
for ideal case

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 Liquid mixtures (Ideal solution)

(a) Raoult’s law provides a relation between the

vapour pressure of a substance and its mole
fraction in a mixture; it is the basis of the
definition of an ideal solution.

(b) Henry’s law provides a relation between the

vapour pressure of a solute and its mole fraction
in a mixture; it is the basis of the definition of an
ideal-dilute solution.
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 Liquid mixtures (Ideal solution)
Pure A in equilibrium with its vapour Mixtures of A, B in equilibrium with vapours

A(g) A(g)+B(g)
 *A   A  RT ln p *A
A(l) A(l)+B(l)
 A   A  RT ln p A
Combine

* pA
 A    RT ln *
A Raoult’s law Ideal solution
pA
p A  x A p *A follow both these
Thus the chemical potential of component equations
of an ideal solution
 A   *A  RT ln x A
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Can be used as definition of ideal solution.
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 Henry’s Law
Henry’s law – vapour pressure of solute is
proportional to its mole fraction (but the
proportionality constant is not vapour pressure
of pure substance)

pB  xB K B
xB is the mole fraction of the solute and KB is an empirical constant
Ideal Dilute Solution - Mixture for which
solvent obeys Raoult’s Law and solute obeys
Henry’s Law
KB has pressure unit. The value of KB can be
obtained by extrapolating the graph to xB =1
In practical Henry’s is expressed

pB  bB K B
bB = molality
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Question; The table below shows vapour pressures of each component of a
mixture of acetone (A) and chloroform (C) at 35 oC.

xc 0 0.20 0.40 0.60 0.80 1.00

pc/kPa 0 4.7 11 18.9 26.7 36.4
pA/kPa 46.3 33.3 23.3 12.3 4.9 0

 Show that the mixture confirms Raoult’s law for component in large excess and
Henry’s law for minor component. Determine Henry’s Law constant.

 Method. Both Raoult’s and Henry’s laws are statements about the form of the
graph of partial vapour pressure against mole fraction. Therefore, plot the partial
vapour pressures against mole fraction. Raoult’s law is tested by comparing the
data with the straight line pJ = xJ P*J for each component in the region which it is in
excess (and acting as the solvent). Henry’s law is tested by finding a straight line
PJ = xJ K*J that is tangent to each partial vapour pressure at low x, where the
component can treated as the solute.

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 Answer.
 The data are plotted in figure
together with the Raoult’s line.

 Henry’s law requires K = 23.3 kPa

For propanone and K = 22.0 kPa for
trichloromethane.

 Notice how the system deviates

from both Raoult’s and Henry’s laws
even for quite small departures from
x = 1 and x = 0, respectively.

 We deal with these deviations in the

solvent and solute activities.

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 Question; Estimate the molar solubility of O2 in water at 25 oC if its
partial pressure is 21 kPa, KO2 , 7.9 x 104 kPa kg mol-1 and rH2O = 0.99709
kg dm-3.

Answer.
For its partial pressure in the atmosphere at sea level, we write;

bO2 = PO2 / KO2 = 21 kPa / 7.9 x 104 kPa/mol = 2.7 x 10-4 mol/kg

The molality of the saturated solution is therefore 0.27 mmol/kg. To

convert this quantity to a molar concentration, we assume that the mass
density of this dilute solution is essentially that of pure water at 25 °C, or
dH2O = 0.99709 kg/dm3. It follows that the molar concentration of oxygen
is;

[O2] = bO2 x dH2O = 0.26 mmol/kg x 0.99709 kg/dm3 = 0.27 mmol/dm3

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Properties of solution

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 Surface tension
• Energy required to increase the surface area of a liquid by a unit
of area.
• How does the energy of the droplet depend on its surface area???
• A molecule at the surface of a liquid experiences only net inward
cohesive forces.
dA = γdσ
Where:
A is the Helmholtz energy
γ is constant of proportionality also called as
the surface tension
σ is the unit element of area

Unit: energy/ area or J m-2

The work, w needed to change the surface

area, σ, of a sample

Definition of surface tension

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36
 Capillary rise
•The rise of a liquid that wets a tube up the inside of a small diameter tube
(i.e., a capillary) immersed in the liquid.
•The liquid creeps up the inside of the tube (as a result of adhesive
forces between the liquid and the inner walls of the tube) until the
adhesive and cohesive forces of the liquid are balanced by the weight of
the liquid.
•The smaller the diameter of the tube, the higher the liquid rises.

The capillary rise is given by:

h= 2γ cos θ/ ρgr 37
 Adhesive Force
•Forces of attraction between a liquid and a solid surface.
•The difference in strength between cohesive forces and adhesive
forces determine the behavior of a liquid in contact with a solid
surface.
• Cohesive forces are the forces that hold liquids
together.
• Adhesive forces are the forces between a liquid and
another surface.
– Capillary rise implies that the:
• Adhesive forces > cohesive forces
– Capillary fall implies that the:
• Cohesive forces > adhesive forces
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 Equation of Young and Laplace
• If in equilibrium a liquid surface is curved, there is a pressure
difference across it
• The surface tension tends to minimize the area
• This result in a planar geometry of the surface,
in order to curve the surface, the pressure on
one side must be larger than on the other
side

Laplace equation

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 Rubber Membrane

• Rubber membrane at the end of cylindrical tube. An

inner pressure Pi can be applied, which is different
than the outside pressure Pa

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• The Young-Laplace equation relates the pressure
difference between the two phase P and the
curvature of the surface

1 1 
P   .  
 R1 R2 
• R1 and R2 are the two principal radii of curvature. P
is also called Laplace pressure, and equation above
also referred to as the Laplace equation

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 Illustration of the curvature of a
cylinder and a sphere

• For a cylinder of radius r a convenient choice is R 1

= r and R2 =  so that the curvature is 1/r + 1/ = 1/r
• For a sphere with radius R we have R1 = R2 and the
curvature is 1/R + 1/R = 2/R

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 DIY
• How large is the pressure in a spherical bubble with a
diameter of 2 mm and a bubble of 20 nm diameter in
pure water, compared with the pressure outside?

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 Fundamental Implications
• If we know the shape of a liquid surface we knows its
curvature and we can calculate the pressure difference

• In the absence of external fields (e.g. gravity) the

pressure is the same everywhere in the liquid;
otherwise there would be a flow of liquid to regions of
low pressure, thus P is constant and Young-Laplace
equation tells us that in this case the surface of the
liquid has the same curvature everywhere

• With the help of Young-Laplace equation it is possible

to calculate the equilibrium shape of a liquid surface
(geometry)

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Application of the Young-Laplace Equation

 Applying Young-Laplace equation to simple

geometries is usually obvious at the side with the
higher pressure.

 For example, in both inside a bubble and inside a

drop, the pressure is higher than outside.

 But in other case, it is not so obvious, because the

curvature can have an opposite sign.

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 For example, a drop hanging between the planar ends of two
cylinders, then the two principal curvatures defined by;
C1 = 1/R1 and C2 = 1/R2

 Thus, it can have a different sign. We count it positive if the

interface is curved towards the liquid.

 The pressure difference is defined as; P = Pliquid - Pgas

Fig. A: A gas bubble in liquid and a

drop in a gaseous environment

Fig. B: A liquid meniscus with radii

of curvature of opposite sign
between two solid cylinders.

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• Colligative properties are properties of solutions
that depend solely on the number of particles
dissolved in the solution.

• Colligative properties do not depend on

the kinds of particles dissolved.

• Colligative properties are a physical property of

solutions

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Among colligative properties are
Vapor pressure lowering

Boiling point elevation

Freezing point depression

Osmotic pressure

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 Vapour Pressure Lowering
 Recall that solutions are homogeneous mixtures of two or
more pure substances.

 In a solution, the solute is dispersed uniformly throughout the

solvent.

 When two substances whose molecules are very similar, form

a liquid solution, the vapor pressure of the mixture is simply
related to the vapor pressures of the pure substances. 49
 Vapor Pressure

 As solute molecules are added to a

solution, the solvent become less
volatile (=decreased vapor pressure).

 This is a result of solute-solvent

interactions.

 Therefore, the vapor pressure of a

solution is lower than that of the pure
solvent.

http://wps.prenhall.com/wps/
media/objects/3312/3391718/
blb1305.html
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 Boiling Point Elevation and
Freezing Point Depression
Solute-solvent interactions also
cause solutions to have higher
boiling points and lower
freezing points than the pure
solvent.

Salt is often used in the winter to

melt ice on the roads.
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 Boiling Point Elevation
The change in boiling
point is proportional to
the molality of the
solution:
Tb = Kb  m

where Kb is the molal

boiling point elevation
constant, a property of
Tb is added to the normal boiling the solvent.
point of the solvent.
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 Freezing Point Depression
• The change in freezing
point can be found
similarly:
Tf = Kf  m

• Here Kf is the molal

freezing point
depression constant of
the solvent.
Tf is subtracted from the normal freezing
point of the solvent.
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 Boiling Point Elevation and
Freezing Point Depression
In both equations, T
does not depend on
T b = K b  m
what the solute is, but
only on how many
particles are
dissolved. Tf = Kf  m

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 Colligative Properties of
Electrolytes
Because these properties depend on the number of particles
dissolved, solutions of electrolytes (which dissociate in
solution) show greater changes than those of
nonelectrolytes.
e.g. NaCl dissociates to form 2 ion particles; its limiting van’t
Hoff factor is 2.

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 Colligative Properties of
Electrolytes
However, a 1 M solution of NaCl does not show
twice the change in freezing point that a 1 M
solution of methanol does.
It doesn’t act like there are really 2 particles.

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van’t Hoff Factor

One mole of NaCl in

water does not
really give rise to
two moles of ions.

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 The van’t Hoff Factor
• Reassociation is more
likely at higher
concentration.
• Therefore, the
number of particles
present is
concentration
dependent.

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 Osmosis
• Semipermeable membranes allow some
particles to pass through while blocking
others.
• In biological systems, most
semipermeable membranes (such as
cell walls) allow water to pass through,
but block solutes.

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 Osmosis
In osmosis, there is
net movement of
solvent from the area
of higher solvent
concentration (lower
solute concentration)
to the are of lower
solvent
concentration (higher
solute concentration).

Water tries to equalize the concentration on both sides until

pressure is too high.

If the osmotic pressure is the same on both sides of a membrane (i.e., the
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concentrations are the same), the solutions are isotonic.
 Osmotic Pressure
• The pressure required to stop osmosis,
known as osmotic pressure, , is

n
=( ) RT = MRT
V
where M is the molarity of the solution

If the osmotic pressure is the same on both sides of a membrane

(i.e., the concentrations are the same), the solutions are isotonic.

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