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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 = ?
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
q = qsurr
2) Surroundings in thermodynamic equilibrium throughout the process
dSsurr
Combining 1) and 2)
qsurr = T q T
dSsurr =
q T
dS
MATERIAL EQUILIBRIUM
dS q T
dU = q + w dU T dS + w
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
MATERIAL EQUILIBRIUM
Ligand binding in biological system
Impact on protein structure and function Drug discovery
Influenza virus
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MATERIAL EQUILIBRIUM
Ligand binding in biological system
Impact on protein structure and function Drug discovery
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
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
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
dS
q T
dG = dH
T dS 0
16
MATERIAL EQUILIBRIUM
Constant T and P
dG = dH T dS 0
dG < 0 dG = 0
spontaneous process
equilibrium
G=
T S
G<0 G=0
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
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
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
A=U
TS
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
24
THERMODYNAMIC RELATIONS
State functions U, S, H, G, A
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)
dS
surroundings
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 +
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
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
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
G=G +G dG = = i = dG
phase
solid
+G
gas
+ =
G i dni
i
dG =
S dT + V dP +
G ni
39
MATERIAL EQUILIBRIUM
k
dG =
SdT + V dP +
i=1
i dni
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
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
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
dG = 0 dG = dG = SdT + V dP +
i
i dni i dni = 0
i
SdT + V dP
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
T,P
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
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
phase
phase equilibrium =
Mechanical, thermal, material equilibrium: chemical potential of each component is everywhere the same (phase equilibrium, closed system, P-V work only)
= i
46
PHASE EQUILIBRIUM
phase Closed system in mechanical and thermal equilibrium, P-V work only, not yet at material equilibrium
phase
dG < 0 S dT + V dP +
i
dG =
i dni
i dni < 0
i
)dn < 0
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 =
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
dni =
i d
i i
d = 0
49
REACTION EQUILIBRIUM
Change in moles of species i
ni = ni
ni,0 =
i dni = 0
i
i i
d = 0
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