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CHEM 579: Course Outline
1. Surface and Colloid Chemistry and Importance
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3. Thermodynamics of Interfaces Fundamentals
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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 }
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y3 dy3 Velocity , ,
y dt dt dt
x3
dx3 {v x3 , v y3 , vz3 } Both notations
x will be used
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
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
{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.
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Internal energy = simply energy = total energy (U)
At a microscopic level, U can have number of forms:
- the internal energy stored in the form of molecular vibrations and rotations
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First Law of Thermodynamics:
- the total energy (U) of the universe cannot change
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
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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
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
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
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)
(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
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
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
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NaOH (s) + HCl(aq.) NaCl(s) + H 2O(l )
S o
m, HCl ( aq.)
1
= 56.5JK mol 1 Smo , H 2O(l ) = 69.91JK 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.
1
r S (25 C ) = 188.83 JK mol 144.71JK mol + 205.138JK 1mol 1
o
m
o 1 1 1 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
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,
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.
U = TS + i Ni + A (1)
dU = TdS + S dT + i dNi + Ni d i + dA + Ad
(2)
Recall the internal energy of surface
0 = Ni d i + Ad
At constant temperature dT = 0, thus
(5)
N i
d = d i = i d i (6)
A
This is known as Gibbs adsorption isotherms for liquid surfaces.
d = 1d 1 2 d 2 (7)
a2
2 =
RT a2 T
Experimental Aspects
Variation of surface tension of aqueous
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Overall Take home messages from Thermo
U G
= =
A S ,V , Ni A T , P , Ni
F a2
= 2 =
A T ,V , Ni RT a2 T
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