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CHEM 579

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You are on page 1of 35

(vthangad@ucalgary.ca)

ES 656 E; Phone: (403) 210 8649

Winter 2017

1

CHEM 579: Course Outline

1. Surface and Colloid Chemistry and Importance

Electrochemistry and non-electrochemical aspects

Surfaces, Adsorption

2

3. Thermodynamics of Interfaces Fundamentals

3

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.

4

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

{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

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

6

Potential Energy, Ep

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

it would take 1 billion years to print 6 6.023 1023 Variables!

7

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.

8

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

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

9

First Law of Thermodynamics:

- the total energy (U) of the universe cannot change

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

in the system equal the heat released + work done

dE = q + w

dU is a state function.

10

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

importance and therefore must be included.

11

(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

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

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

13

Change of a System

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

14

Intensive Variables

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

15

Internal Energy (U)

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

16

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

17

U=q+w

H = U + pV

G = H -TS F = U -TS

18

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

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

20

TAKE HOME EQUATIONS

21

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

22

Calculate the standard reaction entropy for the combustion of methane

to carbon dioxide and liquid water at 25 C.

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

1 1

243JK mol

23

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

24

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

25

Exercise

S R V

2 2 2

An

The energy of a system is given by: U = 2 +

R n n Q

0

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

26

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

27

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 .

12

1 1 V 3 2

Answer: = 2 T

3 A 3

28

Thermodynamic Relationships and Surface Tension

Change in the Internal Energy can be defined using combined first and second

law of thermodynamics,

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

work.

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

Helmholtz free energy

29

Using Gibbs free energy

If pressure is same for both phases

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

30

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

31

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

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)

32

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

a2

2 =

RT a2 T

Component (2).

Experimental Aspects

Variation of surface tension of aqueous

(pentanol)

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.

34

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

35

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