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CHEMISTRY 579 Surface and Colloid

Chemistry for Engineers

VenkataramanThangadurai, PhD, FRSC


(vthangad@ucalgary.ca)

Office hours: TBA; Advance Email (preferred)


ES 656 E; Phone: (403) 210 8649
Winter 2017

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CHEM 579: Course Outline
1. Surface and Colloid Chemistry and Importance

2. Surface Tension/Surface Energy

3. Thermodynamics of Interfaces Fundamentals

4. Practical Applications of Interface Sciences


Electrochemistry and non-electrochemical aspects

5. Experimental Techniques in Interface Science- Solid


Surfaces, Adsorption

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3. Thermodynamics of Interfaces Fundamentals

3.1 Definition of System Variables

3.2 Thermodynamic Potentials

3.3. Thermodynamic definition of Surface Tension

3.4 Gibbs Adsorption Isotherm

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PRINCIPLES
Variables in Thermodynamics
Variables used in any scientific discipline depend upon the scientists
view of nature.
I can see
the molecules

can see
All I thing
s o m e
is
blue!

Maxwells Demon
Molecular View: All natural phenomena must be described in terms
of the position and velocity of each molecule.

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What do we mean by position and velocity?
Consider 1 molecule say # 3 taken out of a mole of molecules:
We put this molecule in a coordinate frame.

z Position {x3 , y3 , z3 }
dz3 But the molecules are in motion
z3 Let this change occur in time dt
dx3 dy3 dz3
{ x!3 , y!3 , z!3 }
3
y3 dy3 Velocity , ,
y dt dt dt
x3
dx3 {v x3 , v y3 , vz3 } Both notations
x will be used

Conclusion: We need 6 Variables/Molecule


{x , y , z , v
3 3 3 x3 , v y 3 , vz 3 }5
1 mole 6 6.023 10 23
variables
6.023 1023 = N A = Avogadro's Number
These variables can be used to describe any property of the system
e.g. Energy U ( x1 , y1 , z1 , vx1 , v y1 , vz1 , x2 , y2 , z2 , vx 2 , v y 2 , vz 2 , ... 6 N variables)
A

= Kinetic Energy EK + Potential Energy EP

Kinetic Energy the energy of motion


Energy can be transferred by moving particles

Collision of fast particles with slower particles causes the slow particle to
speed up while the fast molecule slows

1 1 1 1 1 2 1 ...
= mvx1 + mv y1 + mvz1 + mvx 2 + mv y 2
2 2 2 2
+ mvz22 +
2 2 2 2 2 2
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Potential Energy, Ep

Potential energy increases when: objects that attract move


apart, or objects that repel move toward each other.

Ep = ( x1 , y1 , z1 , x2 , y2 , z2 , ... )
Molecular Variables for 1 mole:

{x , y ,z ,x , y ,z , x! , y! , z! , x! , y! , z! ,...}
1 1 1 2 2 2 1 1 1 2 2 2
Microscopic State

Problem: Given a computer that prints 1 variable every 106 s


it would take 1 billion years to print 6 6.023 1023 Variables!
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Conclusion: Microscopic state or molecular view is too detailed

{x , y ,z ,x , y ,z , x! , y! , z! , x! , y! , z! ,...}
1 1 1 2 2 2 1 1 1 2 2 2
{New Variables}
When we examine a system in the lab. much of the molecular
information is never measured.

Why do you worry?

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Internal energy = simply energy = total energy (U)
At a microscopic level, U can have number of forms:

-the kinetic energy of molecules

- the potential energy of the constituents of the system

- the internal energy stored in the form of molecular vibrations and rotations

- the internal energy stored in the form of chemical bonds

Internal energy is a state function and it does not depend on path.

The internal energy of isolated system is constant, i.e. energy can be


neither created nor destroyed-called as First Law of Thermodynamics.

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First Law of Thermodynamics:
- the total energy (U) of the universe cannot change

Change in energy of universe is zero, i.e., dU = 0.

Two ways energy lost from a system,


(i) converted to heat, q and (ii) used to do work, w

Energy conservation requires that the energy change


in the system equal the heat released + work done

dE = q + w

dU is a state function.

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3. Thermodynamics (Macroscopic)
Use variables that are measured in the laboratory & relevant to system:

(1) Volume V
(2) Area A New Variable
In most problems the surface surrounding a system is too remote
from points within to have any effects on the properties there
Surface
Point
of interest Too far away

variable A has not been so far used

In this course, it is the surface that is of central


importance and therefore must be included.

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(3) Mass m
= Number of different components with masses:
m1 , m2 ....m
Since molar masses M1 , M 2 ...M can be calculated
it is more convenient to use mole numbers:

n1 =
m1 m
, n2 = 2 ... n =
m
M1 M2 M
(4) Charge Q if ions are present
(5) A variable that predicts the direction in which processes occurring
in the system will take place

Entropy S
A process will occur naturally only in the direction of entropy increase

Closing list of macroscopic variables: (V , A, n1, n2 ...n , Q, S )


These variables are now used to express the properties of the system

e.g energy as function of these variables is: E = E (V , A, n1 , n2 ...n , Q


12 , S )
Change of a system:
We start with E = E (V , A,n1 ,n2 ...n ,Q,S )
dE =
E E E
E dV + E dA +

A,{n}, V , n , dn j + dQ + V , dS
V Q ,S A Q ,{S } j =1 n j V{n,}A,n ,Q ,S Q V{n,}A,S, S {n}A,Q,
p j j
T
Pressure Surface Tension Chemical Potential Electrical Temperature
Potential

The notation {n} n j means all the members of the set {n} barring n j .

dE = pdV + dA + j dn j + dQ + TdS
j=1

All the derivatives are the Intensive Variables


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Change of a System

In most chemical and physical processes interest generally lies


in the changes that take place in the variables rather than in
their absolute values. Thus the change in energy is given by:
U = U (V ,n1 ,n2 ...n ,Q,S, A)

U
U U U
dU = dV + dn j + dQ + dS
V {Sn},Q , n Q { } S V ,{n},
j =1 j { } j
n n , V , n , Q
Q,S S

p j T U
+
A V ,{n},
Q,S


dU = pdV + j n j + dQ + TdS + dA
j=1
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Intensive Variables

The variable that does not depend on amount of the substances


are called as Intensive Properties. For example:
U
n ,Q , = p Pressure
V {S }

U
= j Chemical Potential of species j
n j {Qn,}S n j ,

U
= Electrical Potential
Q VS ,{n},

U U
V , n , = T Temperature A V , n , = Surface Tension
{}
S Q { } Q,S

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Internal Energy (U)

dU = TdS - pdV + dn+ dQ

Extensive Intensive Pairing


variable variable relation
U
V p p =
V n ,Q ,S
U
n =
n V ,Q ,S
Q U
=
Q V ,n ,S
S T U
T =
S V ,n ,Q
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Thermodynamics builds a powerful edifice based on these variables
to define the properties of the system. From these primary definitions,
for example, are introduced several related ones:

(1) Enthalpy: H = U + pV
(2) Helmholtz Free Energy: F = U TS
(3) Gibb's Free Energy: G = H TS

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U=q+w
H = U + pV

G = H -TS F = U -TS

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Change in Energy
dE = pdV + dA + j dn j + dQ + TdS
j =1

G = E + pV TS is the Gibb's Free Energy

dG = dE + p dV + V dP - T dS - SdT

dG = dA + j dn j + dQ + Vdp SdT
j =1

G G G G G
{n},Q , = = j = p = V = S
A p ,T n
j QA,,{pn,}T n j , Q A,{n}, Q ,{T }
A , n , T QA,,{pn},
p ,T

For no change in # moles of any neutral species

Free energy simplifies dG = dA + Vdp SdT 19


U=q+w
H = U + pV
F G
S = =
T V ,Q,n T p,Q,n
U F
p= =
V S ,Q,n V T ,Q,n

G H U F
n = = = =
n p,T ,Q n p,Q,S n V ,Q,S n T ,V ,Q
U H
T = =
S V ,Q ,n S p ,Q ,n

H G
V = =
p S ,Q , n p T ,Q ,n

G = H -TS F = U -TS
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TAKE HOME EQUATIONS

dG = Vdp SdT + dA + i dNi

dF = pdV SdT + dA + i dNi

dU = TdS pdV + dA + i dNi

dH = Vdp + TdS + dA + i dNi

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NaOH (s) + HCl(aq.) NaCl(s) + H 2O(l )

Smo , NaOH ( s ) = 64.46 JK 1mol 1 Smo , NaCl ( S ) = 72.13JK 1mol 1

S o
m, HCl ( aq.)
1
= 56.5JK mol 1 Smo , H 2O(l ) = 69.91JK 1mol 1

r S mo (25 o C ) = (72.13 + 69.91) JK 1mol 1 (64.46 + 56.50) JK 1mol 1

r S mo (25 o C ) = 142 .04 JK 1mol 1 121 .16 JK 1mol 1 = 20.88JK 1mol 1

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Calculate the standard reaction entropy for the combustion of methane
to carbon dioxide and liquid water at 25 C.

Solution The reaction is


CH 4 ( g ) + 2O2 ( g ) CO2 ( g ) + 2H 2O (l )

Sm ,CH4 = 186.26 JK 1mol 1 Sm ,O2 = 205.138JK 1mol 1

Sm ,CO2 = 213.74 JK 1mol 1 Sm , H2O = 69.91JK 1mol 1

c Sm (T ) = {213.74 + 2 69.91} {186.26 + 2 ( 205.138 )} =


1 1
243JK mol
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H 2 ( g ) + 0.5O2 ( g ) H 2O( g )
Smo , H 2 = 114.71JK 1mol 1
Smo , H 2O( g ) = 188.83JK 1mol 1
Smo ,O2 = 205.138JK 1mol 1

1
r S (25 C ) = 188.83 JK mol 144.71JK mol + 205.138JK 1mol 1
o
m
o 1 1 1 1

r S mo (25o C ) = 188 .83 JK 1mol 1 217 .279 JK 1mol 1 = 28.389 JK 1mol 1

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Pillars in Thermodynamics
U=q+w F = U -TS
dU = TdS pdV dF = -SdT-pdV
U = U (V, S, A, n) F = F (T, V, A, n)

H = U + pV G = H -TS
dH = Vdp+TdS dG = -SdT +Vdp

H = H (P, S, A, n) G = G (T, P, A, n)
q U q H
CV = = Cp = =
T V T V T p T p
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Exercise
S R V
2 2 2
An
The energy of a system is given by: U = 2 +
R n n Q
0

Where , R,0 and are constants.


2 An2
(a )Calculate the surface tension Answer: =
Q2
( b) Show that the surface tension and chemical potential are related by
Maxwell's relation

4 An 4 An
= =
Answer:
n Q 2 A Q 2
S ,V ,A,Q S ,V ,n,Q



n
= Maxwell's relation
A
S ,V ,A,Q S ,V ,n,Q

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Exercise:

Consider a colloid for which the surface tension, entropy and surface
area are given by the following formulae:
= ap 2 S = bT A = p a,b and are constants
Calculate the Gibb's free energy change, G, when the pressure and temperature
are changed from p = 0 and T = 0 to the values of p and T respectively. Assuming
constant volume.
a 3 b 2
Answer: G = p +Vp T
3 2

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Exercise:
A suspension of oil droplets in water has an internal energy given by
the equation:
S 3 A2
E= a is a constant
V
Calculate the surface tension of the suspension as a function of A,V and T .
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1 1 V 3 2
Answer: = 2 T
3 A 3

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Thermodynamic Relationships and Surface Tension

Change in the Internal Energy can be defined using combined first and second
law of thermodynamics,

dU = TdS PdV + i dNi + dW (work )


In the present case, the work done on the system is surface work and no mechanical
work.

dU = TdS PdV + i dNi + dA


For a given chemical species (i) at constant temperature and volume

dU = TdS + i dNi + i dNi + i dNi + dA


Helmholtz free energy

dF = i dNi + i dNi + i dNi + dA


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Using Gibbs free energy

dG = SdT + V dP + V dP + i dNi + i dNi + dA


If pressure is same for both phases

dG = SdT + VdP + i dNi + i dNi + dA

G
Surface tension can be defined as: =
A T , P , Ni
We can also define using internal energy (U) and Helmholtz energy

U F
= =
A S ,V , Ni
A T ,V , Ni
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Gibbs Adsorption Isotherm
Used to describe change of surface tension upon adsorption of materials.

The internal surface energy can be defined as:

U = TS + i Ni + A (1)

Differentiation of equ. 1 gives,.

dU = TdS + S dT + i dNi + Ni d i + dA + Ad
(2)
Recall the internal energy of surface

dU = TdS + i dNi + dA (3)

Equating equation (2) and (3)


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0 = S dT + Ni d i + Ad (4)

0 = Ni d i + Ad
At constant temperature dT = 0, thus

(5)

Equation 5 can be rearranged into

N i
d = d i = i d i (6)
A
This is known as Gibbs adsorption isotherms for liquid surfaces.

For two components system, equation 6 can be written as

d = 1d 1 2 d 2 (7)

For an ideal interface d = 2(1) d 2 (8)


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Using the chemical potential definition, equation 8 can be modified as

a2
2 =
RT a2 T

Where R is the gas constant, T is the temperature and a is the activity of


Component (2).

The surface tension decreases with increasing solution concentrations.

Experimental Aspects
Variation of surface tension of aqueous

(a) Amphiphilic substance (SDS)

(b) Hydrophobic or Lyophilic substance


(pentanol)

(c) Hydrophilic substance 33


Exercise question: The surface tension of water with a mole
fraction of 0.001, 0.002, 0.003, 0.004, 0.005, 0.006 and 0.007
of iso-propanol is 67.4, 64.4, 61.9, 59.7,57.7, 55.8 and 54.1
mN/m at 25 oC, respectively. Estimate the surface excess
concentration of propanol at a mole fractions of 0.002, 0.004
and 0.006.

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Overall Take home messages from Thermo

dU = TdS pdV + dA + i dNi

U G
= =
A S ,V , Ni A T , P , Ni

F a2
= 2 =
A T ,V , Ni RT a2 T

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