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Gibbs Energy and Chemical Potentials
Calculation of TunivS two system parametersrS rH
Define system parameters that determine if a given process will be spontaneous?
2
Distinguish between a reversible and an irreversible transformation.
3
revsurr dqdST
Tdq
Sd irrevsurr
From the first law
4
dwdqdU
dwdUdSTsurr
Our definition of work can be extended to include other types of work.
• Electrical work.
• Surface expansion.
• Stress-strain work.
dw=-Pext dV+dwa
where dwa includes all other types of work
5
For a general system
6
0ext e surrdU P dV dw T dS
In an isolated system where dq=0; dw=0; dU=0
dS 0 Now allow the system to make thermal
contact with the surroundings. For an isentropic process (dS = 0)
dU 0
7
For a systems where the temperature is constant and equal to Tsurr
8
0 dwTdSdU
Define the Helmholtz energy A
A(T,V) =U – TS Note that for an isothermal process
dA dw
A w For an isochoric, isothermal process
A 0
9
The Helmholtz energy is a function of the temperature and volume
10
dVVA
dTTA
dATV
PVA
T
STA
V
For an ideal gas undergoing an isothermal volume change
11
1
2ln
2
1
2
1
VV
nRT
PdVdVVA
AV
V
V
V T
For an isothermal, isobaric transformation
12
0ext adU TdS P dV dw
0adU TdS PdV dw
Define the Gibbs energy G
G(T,P) =U – TS+PV Note that for an isothermal process
dG dwa
G wa
For an isothermal, isobaric process
G 0
13
The Gibbs energy is a function of temperature and pressure
14
P T
G GdG dT dP
T P
P
GS
T T
GV
P
For an ideal gas undergoing an isothermal pressure change
15
1
2ln
2
1
2
1
PP
nRT
VdPdPPG
GV
V
P
P T
Define the chemical potential = G/n
16
1
212 lnPP
RTn
GGnG
1
212 ln
PP
RT
For P1 = P = 1 bar, we define the standard state chemical potential
°= (T, 1bar)
17
barP
RTbarTT 1
ln) 1 ,()(
Solids and liquids are essentially incompressible
18
PVPPV
VdPGGGP
P
)( 12
12
2
1
Under isochoric conditions
19
dTSdTTA
AT
T
T
T V
2
1
2
1
SdTdTTA
dAV
Consider the calculation of Helmholtz energy changes at various temperatures
20
dTSTATAT
T
2
1
12
1212 TTSTATA
Under isobaric conditions
21
dTSdTTG
GT
T
T
T P
2
1
2
1
SdTdTTG
dGP
The Gibbs energy changes can be calculated at various temperatures
22
dTSTGTGT
T
2
1
12
1212 TTSTGTG
The Gibbs-Helmholtz relationship
23
2 TH
TT
G
P
2 TH
TT
G
P
Differentiating the chemical potential with temperature
24
JmP
J ST ,
PPRTSTS
JmJm ln,,
For a reversible process
dU = TdS – PdV The Fundamental Equation of
Thermodynamics!! Internal energy is a function of entropy
and volume
25
The total differential
26
dVVU
dSSU
dUSV
PVU
S
TSU
V
The systems is described by • Mechanical properties (P,V)
• Three thermodynamic properties (S, T, U)
• Three convenience variables (H, A, G)
27
The Maxwell relationships are simply consequences of the properties of exact differentials • The equality of mixed partials
28
VS SP
VT
Obtain relationships between the internal energy and the enthalpy
29
PVS
TVU
TT
The Thermodynamic Equation of State!!
A simple relationship between (H/P)T and other parameters.
30
TT PS
TVPH
VdpSdTdG
For a system at fixed composition
...2
,,2
1
,,1
dnnG
dnnG
VdpSdTdG
j
j
nPT
nPT
If the composition of the system varies
KnPTJJ n
G
,,
Using the chemical potential definition
J
JJ dnVdpSdTdG
JO
JJ pRTT ln
Chemical potential is an intensive property For an ideal gas
Note - J (T) is the Standard State Chemical Potential
of substance J
pxRTT JO
JJ ln
The chemical potential of any gas in a mixture is related to its mole fraction in the mixture
Jpure
JJ xRTTp ln,
JJJ
J
OJJJmix
xnRT
nG
ln
In a non-reacting mixture, the chemical potentials are calculated as above.
The total Gibbs energy of the mixture
0
ln
ln
mixmix
JJJ
mixmix
JJJ
J
OJJJmix
VH
xnRTG
S
xnRT
nG
In an ideal gas mixture
J
JJ A0
Consider a closed system at constant pressure
The system consists of several reacting species governed by
J
JJ dndG
At constant T and P, the Gibbs energy change results from the composition change in the reacting system
JOJJ nn
Suppose we start the reaction with an initial amount of substance J
• nJ0
Allow the reaction to advance by moles - the extent of reaction
Examine the derivative of the Gibbs energy with the reaction extent
JJJ
PT
GG
,
G – the non-standard Gibbs energy change
0,
PT
GG
The equilibrium condition for any chemical reaction or phase change
0
eqJJJG
For the simple reaction
Extent of Reaction,
GA*
GB*
Pure components
0
maxmin
A (g) ⇌ B (g)
Adding in the contribution from mixG.
Extent of Reaction,
GA*
GB*
Pure components
0
Mixing Contribution
maxmin
The Gibbs energy of reaction.
Extent of Reaction,
GA*
GB*
min
Pure components
0rG
max
eq
DDD pRTG ln
For the reaction
aA (g) + bB (g) pP (g) + qQ (g)⇌
AAA pRTG ln
BBB pRTG ln
CCC pRTG ln
bB
aA
dD
cC
rrpp
ppRTGG ln
The Gibbs energy change can be written as follows
The Gibbs energy change for a chemical reaction?
47
fG = Jø = the molar formation
Gibbs energy (chemical potential) of the substance
J
oJJ
JfJr JGG
Define the reaction quotient
c d
C Da b
A B
p pQ
p p
lnr rG G RT Q
At equilibrium, rG = 0
eq
eq
c d
C Deq a b
A B
p pK Q
p p
0 ln
eqrG RT Q
At equilibrium, the non-standard Gibbs energy change is 0.
lnr eqG RT K
0 lnr eqG RT K
molkJelements 0
Examine the following reaction
CO2 (g) – C (s) – ½ O2 (g) = 0 The standard state chemical potentials for the
elements in their stable state of aggregation
J
Jr JG
sCgOgCOGr 22
gCOgCOGf 22
JJGf
Note – since the (elements) = 0 kJ/mol
In general
RTG
K rP
ln
We can write the equilibrium constant as
dT
TGd
RdTKd
r
P
1ln
Differentiating
J
Jr JG
dT
TJ
d
RdTKd J J
P
1ln
2T
HdT
TGd
2TH
dT
TGd
r
r
For a chemical reaction, with a standard Gibbs
energy change, rG
2
lnRT
HdT
Kd rP
The van’t Hoff equation relates the temperature dependence of Kp to the reaction enthalpy change
2
1
2
1
2
ln
ln
2
ln
ln
T
T
r
K
KP
rP
dTRT
HKd
dTRT
HKd
P
P
Assuming the reaction enthalpy change is constant with temperature
121,
2, 11ln
TTRH
K
Kr
P
P
If the enthalpy change for the reaction is know, we can estimate the Kp value at any temperature
reaction
y = -6937.6x - 8.9829-35.00-34.50-34.00-33.50-33.00-32.50-32.00-31.50-31.00-30.50-30.00
0.003 0.0032 0.0034 0.0036 0.0038
1/T (K-1)
ln K
w
H2O (l) ⇌H+ (aq) + OH- (aq)
Revisit the Gibbs energy profile!
Extent of Reaction,
GA*
GB*
0
maxmin
rG = 0
At equilibrium, the Gibbs energy is at a minimum
The second derivative of the Gibbs energy with the extent of reaction,
= G’’ is positive!!
PT
G
,2
2
The change in the extent of reaction with temperature.
T / K
max
min
rHo >0
rHo < 0
The change in the extent of reaction with pressure.
P / bar
max
min
rVo < 0
rVo > 0