Sie sind auf Seite 1von 50

CHAPTER 4

Material Equilibrium

MATERIAL EQUILIBRIUM
In each phase of a closed system, the number of moles of each substance present remains constant in time 1) reaction equilibrium 2) phase equilibrium

Isolated system If not at material equilibrium, chemical reactions or transport of matter between phases will occur

S>0
Equilibrium = ?

system matter energy

dS

surroundings

S = max

dS = 0
2

MATERIAL EQUILIBRIUM
Not all systems are isolated! The whole universe is isolated:

Suniv =

S+ dS

Ssurr dSsurr

dS + dSsurr

MATERIAL EQUILIBRIUM
dS
How can we calculate

dSsurr

Ssurr ?

From now on we assume (if the system is not isolated) 1) Surroundings (big) at constant volume 2) System and surroundings are in thermal equilibrium at T (closed) Infinitesimal transfer of heat -q from the system to surroundings system q Surroundings in thermodynamic equilibrium throughout the process surroundings

q = qsurr

dS

dSsurr

qsurr = T
4

MATERIAL EQUILIBRIUM
dS dSsurr

1) Infinitesimal transfer of heat -q from the system to surroundings

q = qsurr
2) Surroundings in thermodynamic equilibrium throughout the process

dSsurr
Combining 1) and 2)

qsurr = T q T

dSsurr =

q T

dS

material change, closed system in mechanical and thermal equilibrium


5

MATERIAL EQUILIBRIUM
dS q T

material change, closed system in mechanical and thermal equilibrium

dU = q + w dU T dS + w

material change, closed system in mechanical and thermal equilibrium


6

MATERIAL EQUILIBRIUM
q dS = > T
ice melting water/ice water at at 10+10 0 C C C

MATERIAL EQUILIBRIUM
dS q T

q dS = T

Equilibrium

MATERIAL EQUILIBRIUM
dS q T

Re-state this condition more conveniently in terms of new state functions (G, A) 1) Focus on systems in thermal and mechanical equilibrium (sys + surr have same T and P) 2) Combine 1st and 2nd law

More specifically, a) T and V are fixed (e.g., chemical reactions including gases in a closed container) b) T and P are fixed (e.g., reactions in liquid or phase changes at atmospheric pressure)

MATERIAL EQUILIBRIUM
Chemical reactions on atmospheric aerosols

Impact on cloud formation Ozone concentration Atmosphere chemical composition

Center for Aerosol Impacts on Climate and the Environment

HCl dissociation on ice surfaces in the stratosphere


10

MATERIAL EQUILIBRIUM
Ligand binding in biological system

Impact on protein structure and function Drug discovery

Center for Theoretical Biological Physics

Influenza virus
11

MATERIAL EQUILIBRIUM
Ligand binding in biological system

Impact on protein structure and function Drug discovery

Center for Theoretical Biological Physics

Influenza virus: Tamiflu effects


12

MATERIAL EQUILIBRIUM
Physicochemical processes in porous materials

Gas adsorption and separation Carbon capture Drug delivery Molecular transport

Metal-organic frameworks
13

MATERIAL EQUILIBRIUM
Physicochemical processes in porous materials

Gas adsorption and separation Carbon capture Drug delivery Molecular transport

Metal-organic frameworks: Benzene adsorption


14

MATERIAL EQUILIBRIUM
Constant T and P

System and surroundings are in mechanical and thermal equilibrium Only P-V work is possible

G = U + PV

TS = H

TS

Gibbs free energy

Interesting...

dS

q T

dS

q = dH
P = constant

dH T
15

MATERIAL EQUILIBRIUM
Constant T and P

System and surroundings are in mechanical and thermal equilibrium Only P-V work is possible

G = U + PV

TS = H

TS

Gibbs free energy

dS

q T

dG = dH

T dS 0

16

MATERIAL EQUILIBRIUM
Constant T and P
dG = dH T dS 0

Material equilibrium at constant P and T

dG < 0 dG = 0

spontaneous process

equilibrium

At constant T, we can integrate

G=

T S

G<0 G=0

spontaneous process equilibrium


17

MATERIAL EQUILIBRIUM
Constant T and P
dG = dH T dS 0

The spontaneity of a process depends on the trade-off between enthalpy and entropy (times T) changes

Clearly, if

H S

decreases spontaneous process!!! increases

18

MATERIAL EQUILIBRIUM
Constant T and P

System and surroundings are in mechanical and thermal equilibrium Only P-V work is possible

G = U + PV

TS = H

TS

dG = dU + P dV + V dP
dU = q + w = q Pext dV + wother

T dS

SdT

dG = dH + wother

T dS
19

MATERIAL EQUILIBRIUM
Constant T and P

System and surroundings are in mechanical and thermal equilibrium Only P-V work is possible

dG = dH + wother G= H T S + wother G G wother = H G

T dS wother = H T S

T S0 G wother

wother

-G is the maximum non-PV work that a closed system can do on the surroundings at constant P and T
20

MATERIAL EQUILIBRIUM
Constant T and V

System and surroundings are in mechanical and thermal equilibrium

A=U

TS

Helmotz free energy

dS

q T

dA = dU

T dS 0
21

MATERIAL EQUILIBRIUM
Constant T and V

System and surroundings are in mechanical and thermal equilibrium Possibility to do work other than P-V work

dA = dU

T dS 0

dA = q + wother

T dS

dA

wother = q

T dS 0
22

MATERIAL EQUILIBRIUM
Constant T and V

System and surroundings are in mechanical and thermal equilibrium Possibility to do work other than P-V work

dA

wother = q

T dS 0

A A wother

wother 0 A wother

-A is the maximum work that a closed system can do on the surroundings at constant V and T
23

THERMODYNAMIC RELATIONS
State functions U, S, H, G, A
closed system reversible process P-V work only

dU = q + w

dU = T dS

P dV

H = U + PV
Enthalpy free energy

G=H

TS

A=U

TS

Gibbs free energy

Helmotz free energy

24

THERMODYNAMIC RELATIONS
State functions U, S, H, G, A

Heat capacities closed system P-V work only

Thermal expansion

CV =

U T H T

=T
V

S T S T

1 = V
V

V T

Isothermal compressibility

CP =

=T
P

=
P

1 V

V P

25

THERMODYNAMIC RELATIONS
Gibbs and Maxwell equations

Consequences of 1st law and thermodynamic conditions Closed system P-V work only Reversible process

dU = T dS U V U S V
2

P dV U S =T
V

=
S 2

U V S

P S

=
V

T V

S
26

THERMODYNAMIC RELATIONS
Gibbs and Maxwell equations

Consequences of 1st law and thermodynamic conditions Closed system P-V work only Reversible process

dH = T dS + V dP H P H S P
2

=V
S 2

H S V S

=T
P

H P S

=
P

T P

S
27

THERMODYNAMIC RELATIONS
Gibbs and Maxwell equations

Consequences of 1st law and thermodynamic conditions Closed system P-V work only Reversible process

dG = G T G T P
2

SdT + V dP G P =V
T

=
P 2

G P T

S P

=
T

V T

P
28

THERMODYNAMIC RELATIONS
Gibbs and Maxwell equations

Consequences of 1st law and thermodynamic conditions Closed system P-V work only Reversible process

dA = A T A T V
2

SdT

P dV A V =
T

=
V 2

A V T

S V

=
T

P T

V
29

MATERIAL EQUILIBRIUM
In each phase of a closed system, the number of moles of each substance present remains constant in time Universe (isolated)

dU = T dS
closed system energy

P dV

dH = T dS + V dP
matter

dG =
surroundings

SdT + V dP SdT P dV

dS

dA =
System & surroundings in thermal and mechanical equilibrium (same T and P)

30

MATERIAL EQUILIBRIUM
The composition is changing due to exchange of matter with the surroundings and / or to irreversible chemical reactions and / or phase changes Universe (isolated)

dU = T dS

P dV

dH = T dS + V dP
matter energy

dG =
surroundings

SdT + V dP SdT P dV

dS

dA =
System & surroundings in thermal and mechanical equilibrium (same T and P)

31

MATERIAL EQUILIBRIUM
The composition is changing due to exchange of matter with the surroundings and / or to irreversible chemical reactions and / or phase changes Universe (isolated)

dU = T dS
reactions phase changes

P dV

dH = T dS + V dP dG =
surroundings

dS

energy

SdT + V dP SdT P dV

dA =
System & surroundings in thermal and mechanical equilibrium (same T and P)

32

MATERIAL EQUILIBRIUM
The composition is changing due to exchange of matter with the surroundings and / or to irreversible chemical reactions and / or phase changes Universe (isolated)

dU = T dS
reactions phase changes matter energy

P dV

dH = T dS + V dP dG =
surroundings

SdT + V dP SdT P dV

dS

dA =
System & surroundings in thermal and mechanical equilibrium (same T and P)

33

MATERIAL EQUILIBRIUM
The composition is changing due to exchange of matter with the surroundings and / or to irreversible chemical reactions and / or phase changes Universe (isolated)

reactions phase changes matter energy

U, H, A and G are functions of T, P and ni

dS

surroundings

System & surroundings in thermal and mechanical equilibrium (same T and P)

34

MATERIAL EQUILIBRIUM
The composition is changing due to exchange of matter with the surroundings and / or to irreversible chemical reactions and / or phase changes At T and P constant, it is very convenient work with the Gibbs free energy assuming a one-phase system for now

G = G(T, P, n1 , . . . , nk )
dG = G T dT +
P,ni

G P

dP +
T,ni

G n1

P,T,nj =1

dn1 + +

G nk

dnk
P,T,nj =k

dG =
dG =

SdT + V dP
SdT + V dP +

reversible process, closed system, P-V work only

G n1

P,T,nj =1

dn1 + +

G nk

dnk
P,T,nj =k
35

MATERIAL EQUILIBRIUM
dG = SdT + V dP + G n1 dn1 + + G nk dnk
P,T,nj =k

P,T,nj =1

dG =

SdT + V dP +

k i=1

G ni

dni
P,T,nj =i

i =

G ni

chemical potential (one-phase system)

P,T,nj =i

36

MATERIAL EQUILIBRIUM
dG = SdT + V dP +
k i=1

G ni

dni
P,T,nj =i

i =

G ni

P,T,nj =i

Key equation of chemical thermodynamics


k

dG =

SdT + V dP +
i=1

i dni

Chemical reactions in system, transport of matter in or out of system One phase, thermal + mechanical equilibrium, P-V work only dni can be positive or negative
37

MATERIAL EQUILIBRIUM
k

dG =

SdT + V dP +
i=1

i dni

dU = T dS

P dV +
i=1 k

i dni

dH = T dS + V dP +
i=1

i dni

dA =

SdT

P dV +
i=1

i dni
38

MATERIAL EQUILIBRIUM
k

dG =

SdT + V dP +
i=1

i dni

What happens if we have to deal with a multicomponent system?


The state functions U, H, A and G are extensive

G=G +G dG = = i = dG
phase

solid

+G

gas

+ =

G i dni
i

dG =

S dT + V dP +

G ni

chemical potential of species i in phase

39

MATERIAL EQUILIBRIUM
k

dG =

SdT + V dP +
i=1

i dni

What happens if we have to deal with a multicomponent system?


The state functions U, H, A and G are extensive

G=G +G dG = dG

solid

+G

gas

+ =

G i dni
i

dG = S dT +

S dT + V dP + V dP +

dG =

i dni

i system in mechanical and thermal equilibrium P-V work only multiple phases
40

MATERIAL EQUILIBRIUM
dG = S dT + V dP +
i

i dni

What is the condition for material equilibrium?


If P,T are constant and the system is closed we showed that at equilibrium

dG = 0

i dni = 0
i

material equilibrium P-V work only thermal and mechanical equilibrium closed system P and T constant
41

MATERIAL EQUILIBRIUM
dA = S dT P dV +
i

i dni

What is the condition for material equilibrium?


If V,T are constant and the system is closed we showed that at equilibrium

dA = 0

i dni = 0
i

material equilibrium P-V work only thermal and mechanical equilibrium closed system V and T constant
42

MATERIAL EQUILIBRIUM

material equilibrium reversible process P-V work only thermal and mechanical equilibrium closed system independent of how equilibrium is reached

i dni = 0
i

Infinitesimal reversible process, closed system, P-V work only

dG = 0 dG = dG = SdT + V dP +
i

i dni i dni = 0
i

SdT + V dP

from Gibbs equations


43

CHEMICAL POTENTIAL
Change in free energy when we add a tiny amount of species i to phase with everything else being held fixed

i (T , P , n1 , n2 , . . . ) =

G ni G n

T ,P ,nj =i

For a pure substance in one phase:

T,P

For substance i in a mixture: (everything in one phase)

i =

G ni

T,P,ni=j

is intensive
44

PHASE EQUILIBRIUM
Closed system in mechanical and thermal equilibrium, P-V work only

phase

P =P T =T

The system reaches material equilibrium. How do you test it?

phase

n = n = n

dn = ( dn) + (dn) = 0

)dn = 0
45

PHASE EQUILIBRIUM
Closed system in mechanical and thermal equilibrium, P-V work only

phase

P =P T =T

The system reaches material equilibrium. How do you test it?

phase

phase equilibrium =
Mechanical, thermal, material equilibrium: chemical potential of each component is everywhere the same (phase equilibrium, closed system, P-V work only)

if more than one component: i

= i
46

PHASE EQUILIBRIUM
phase Closed system in mechanical and thermal equilibrium, P-V work only, not yet at material equilibrium

phase

matter is still flowing around from one phase to another

dG < 0 S dT + V dP +
i

dG =

i dni

i dni < 0
i

)dn < 0

matter flows from higher to lower chemical potential


47

REACTION EQUILIBRIUM
aA1 + bA2 + 0 aA1 bA2 eAm + f Am+1 + . . . + eAm + f Am+1 + . . .

stoichiometric coefficients

1 2

= =

a b

= +e = +f

0
i

i Ai

m+1

a reaction in which v1 moles of A1 are used up will use up v1 moles of A2 and produce vm moles of Am and vm+1 moles of Am+1 = extent of reaction (can be positive or negative)
48

REACTION EQUILIBRIUM
Change in moles of species i

ni = ni

ni,0 =

condition for material equilibrium for any closed system

i dni = 0
i

i = i 0=
i

same chemical potential in all phases at equilibrium dni = change in the total number of moles i in closed system

dni

0=
i

i dni

for an infinitesimal change

dni =

i d

i i

d = 0
49

REACTION EQUILIBRIUM
Change in moles of species i

ni = ni

ni,0 =

condition for material equilibrium for any closed system

i dni = 0
i

i i

d = 0

chemical potential of reactants and products balance

reaction equilibrium

i i i

=0

depends on T, P, and composition. changes as rxn proceeds until the values that satisfy the equilibrium condition are reached. At that point rxn stops.
50

Das könnte Ihnen auch gefallen