Fundamental Concepts
of Thermodynamics
CY11003 – Week 4
Variation of Gibbs free energy with T and p
dG Vdp SdT G G
S V
The Fundamental Equation of T p p T
Chemical Thermodynamics
p2
Gm
V dp
p1
m
RT ln( p2 / p1)
Gm Vmp
Swagata Dasgupta, Chemistry IIT Kharagpur 1
Temperature dependence of Gibbs Energy
Or Gibbs-Helmholtz Equations
𝜕𝐺
𝐺 𝐻 𝑇𝑆 𝑆 𝐺 𝐻 /𝑇
𝜕𝑇
𝜕 𝐺/𝑇 𝜕 𝐺/𝑇
? ?
𝜕𝑇 𝜕 1/𝑇
𝜕 𝐺/𝑇 𝐻 𝜕 𝐺/𝑇
𝐻
𝜕𝑇 𝑇 𝜕 1/𝑇
𝜕 Δ𝐺/𝑇 Δ𝐻 𝜕 Δ𝐺/𝑇
Δ𝐻 If we know H of a
𝜕𝑇 𝑇 𝜕 1/𝑇
process, we can know
how G/T varies with T.
Gibbs-Helmholtz Equations
Fundamental Equations of Thermodynamics or Gibbs Equations - Revisited
𝜕𝑈
𝑑𝑈 𝑇𝑑𝑆 𝑝𝑑𝑉 𝜇 𝑑𝑛 where, 𝜇
𝜕𝑛 , , Applicable to
𝜕𝐻 single phase
𝑑𝐻 𝑇𝑑𝑆 𝑉𝑑𝑝 𝜇 𝑑𝑛 where, 𝜇 multi-component
𝜕𝑛 , , open system in
𝜕𝐴 thermal and
𝑑𝐴 𝑆𝑑𝑇 𝑝𝑑𝑉 𝜇 𝑑𝑛 where, 𝜇 mechanical
𝜕𝑛 , ,
equilibrium and
𝜕𝐺 pV work only.
𝑑𝐺 𝑆𝑑𝑇 𝑉𝑑𝑝 𝜇 𝑑𝑛 where, 𝜇
𝜕𝑛 , ,
𝜕𝑈 𝜕𝐻 𝜕𝐴 𝜕𝐺
𝜇
𝜕𝑛 , ,
𝜕𝑛 , ,
𝜕𝑛 , ,
𝜕𝑛 , ,
Swagata Dasgupta, Chemistry IIT Kharagpur 2
Multi-phase Multi-Component System:
For one phase () system,
dG V dp S dT i dn i
i
in thermal and mechanical
equilibrium pV work only
For multiple phases
dG dG V dp S dT i dn i
i
G
i
Since, S and V are extensive properties, ni p , T , nji
dG Vdp SdT i dn i
Thermal and mechanical
equilibrium. p-V work only
i
Chemical Potential 𝜕𝐺
𝑑𝐺 𝑉𝑑𝑝 𝑆𝑑𝑇 𝑑𝑛
𝜕𝑛 , ,
𝑑𝐺 𝑉𝑑𝑝 𝑆𝑑𝑇 𝜇 𝑑𝑛
Applicable to single phase, multi component
𝜇 𝑓 𝑇, 𝑝, 𝑛 , 𝑛 , ..... system at thermal and mechanical
equilibrium but not material equilibrium.
𝜕𝐺
𝜇 𝑑𝐺 𝜇 𝑑𝑛
𝜕𝑛 , ,
,
#
𝑑𝑤add,max 𝜇 𝑑𝑛
For a pure substance Maximum additional work that
(Chemical Potential) = Gm = G/n can arise from changing the
components of the system.
Swagata Dasgupta, Chemistry IIT Kharagpur 3
Chemical Potential and Phase Equilibrium
Chemical potential for a component in a mixture: G
i
ni p ,T ,n j
(Chemical Potential) for pure substance = Gm = G/n
Chemical potential for substance in
the phases that are in equilibrium
i (p, T) = i (p, T)
At equilibrium, the chemical potential of a substance in the same
throughout a sample, regardless of how many phases are present.
Location and shape of phase boundary
For point “a”
One component (pure) system
(p, T) = (p, T)
For point “b”
(p+dp, T+dT) = (p+dp, T+dT)
(p, T) + d = (p, T) + d
d = d
d Vm dp S m dT
Vm dp – Sm dT = Vm dp – Sm dT
dp/dT = (Sm - Sm) / (Vm – Vm)
The Clapeyron
Equation
dp/dT = Sm,trs /Vm, trs
dT/dp = Vtrs /Strs Applies to any phase
equilibrium of any pure
dp/dT = Strs /Vtrs
substance.
Swagata Dasgupta, Chemistry IIT Kharagpur 4
Location and shape of phase boundary
One component (pure) system
Clapeyron Equation dT/dp = Vtrs /Strs
T1 Vfus
Solid to Liquid Phase Boundary
T p
H fus
dp H vap H vap
Liquid to Vapor Phase Boundary
dT TVm T ( RT ) / p
d ln p H vap
Clausius -Clapeyron Equation
dT RT 2
For Solid to Vapor
d ln p H sub H fus H vap
dT RT 2 RT 2
Temperature Dependence of Chemical Potential:
dG Vdp SdT
d VmdP SmdT
Sm
T P
S m (solid) S m (liquid) S m (gas)
Swagata Dasgupta, Chemistry IIT Kharagpur 5
(isothermal) Pressure dependence of Chemical Potential
G p
p Vdp
G p
G p
2
2 2
V dG Vdp G2 G1
p T 1 1 1
p2
for one component system, 2 (T ) 1 (T ) Vmdp
p1
Case 1: liquid or solid; V weakly dependent on p
2 (T ) 1 (T ) Vm ( p2 p1 ) for one component
system
Case 2: ideal gas; V is dependent on p,
p2
2 (T ) 1 (T ) RT ln
p1
p o = standard chemical potential, the
(T ) o (T ) RT ln chemical potential of the pure
po gas at 1 bar at temp T.
(T ) o (T ) RT ln p p expressed in bar.
Chemical Potential of an ideal gas
p2 p
2 1
p1
Vm dp (T ) o (T ) RT ln
po
Swagata Dasgupta, Chemistry IIT Kharagpur 6
Equilibrium: the extent of a reaction
Yields of reactions may be lower due to reversibility of the chemical reactions:
some reactions may produce only 70% of the product
Equilibrium looks at the extent of a chemical reaction.
Extent of reaction (ξ): dni
d
i
The advantage of using ξ - unique rate of a given reaction.
The major drawback - ξ is an extensive variable and is
proportional to the mass of the system.
The fractional conversion is an intensive measure of the
progress of a reaction.
Extent of reaction (ξ): A B
dG A d B d d of moles of A is converted to B
dnA = - d
G
B A dnB = d
p ,T
Reaction Gibbs energy
G
Gr = extent of reaction
p ,T
the forward reaction is
Gr 0 spontaneous - exergonic
the reverse reaction is
Gr 0 spontaneous - endergonic
Gr 0 the reaction is at equilibrium
Swagata Dasgupta, Chemistry IIT Kharagpur 7
Reaction Gibbs Energy (rG)
𝐴 ⇌ 𝐵
𝑡 0 1 0
d is the extent of reaction.
𝑡 𝑡 1 𝑑𝜉 𝑑𝜉
𝑑𝑛 𝑑𝜉 𝑑𝜉
𝑑𝐺 𝜇 𝑑𝑛 𝜇 𝑑𝑛 𝜇 𝑑𝜉 𝜇 𝑑𝜉 𝜇 𝜇 𝑑𝜉
𝜕𝐺
𝜇 𝜇
𝜕𝜉 ,
The reaction Gibbs energy is the
𝜕𝐺 difference between the chemical potential
Δ 𝐺 𝜇 𝜇
𝜕𝜉 ,
of product and reactant at the
composition of the reaction mixture.
Reaction Gibbs Energy (rG)
𝑎𝐴 𝑏𝐵 → 𝑐𝐶 𝑑𝐷
𝜕𝐺 exergonic
Δ 𝐺 𝑐𝜇 𝑑𝜇 𝑎𝜇 𝑏𝜇
𝜕𝜉 ,
endergonic
𝜕𝐺
Δ 𝐺 𝜈𝜇
𝜕𝜉 ,
CH g 2O g → CO g 2H O 𝑙
Δ 𝐺 2𝜇 𝜇 𝜇 2𝜇
At equilibrium
𝜇𝜈 0 Condition for chemical reaction equilibrium
At the reaction equilibrium, the chemical potentials of the
product balance those of the reactants
Swagata Dasgupta, Chemistry IIT Kharagpur 8
Free Energy Versus Extent of Reaction
G0 < 0 G0 > 0
Reaction Equilibrium
Δ 𝐺 𝜈𝜇 𝜈 𝜇 𝑇 𝑅𝑇 ln 𝑎 𝜈𝜇 𝑇 𝑅𝑇 ln 𝑎
Δ 𝐺 𝑇 Δ 𝐺 𝑇 𝑅𝑇 ln 𝑎 Δ 𝐺 𝑇 𝑅𝑇 ln 𝑄
At equilibrium,
Q a
i
i
i
The reaction Quotient
Thermodynamic (at any extent of the reaction)
𝐾 𝑎
equilibrium constant
at equilibrium
𝜟𝒓 𝑮𝟎 𝑹𝑻 𝐥𝐧 𝑲
Δ 𝐺 𝑇 0 Δ 𝐺 𝑇 𝑅𝑇 ln 𝐾
Practically ai approximated by numerical values of molalities / Can be used to calculate
equilibrium constant for any
by molar concentration / numerical values of partial pressures reaction from tables of
thermodynamic data.
Swagata Dasgupta, Chemistry IIT Kharagpur 9
Reaction Equilibrium in ideal gas reaction
𝑎𝐴 𝑔 𝑏𝐵 𝑔 → 𝑐𝐶 𝑔 𝑑𝐷 𝑔 Δ 𝐺 𝑇 Δ 𝐺 𝑇 𝑅𝑇 ln 𝑄
𝑝 The reaction Quotient in terms of partial
𝑄 𝑎 pressure (at any extent of reaction)
𝑝 p0 = 1 bar
At equilibrium,
𝑝
𝐾 at equilibrium
𝑝
Δ 𝐺 𝑇 0 Δ 𝐺 𝑇 𝑅𝑇 ln 𝐾
𝜟𝒓 𝑮𝟎 𝑹𝑻 𝐥𝐧 𝑲𝒑
Different types of equilibrium constants
Thermodynamic equilibrium constant in terms of activity
𝐾 𝑎
coefficients (ai)
Standard equilibrium constant for gaseous reaction
𝐾 𝑝 pi (in bar units)
𝐾 𝑐 Standard concentration equilibrium constant.
ci in mol/L
𝐾 𝑥 Mole-fraction equilibrium constant
Swagata Dasgupta, Chemistry IIT Kharagpur 10
Temperature dependence of equilibrium constant
r G 0 RT ln K
d ln K
0
1 d rG / T
dT R dT
d rG0 / T H r
0
(Gibbs Helmholtz Equation)
dT T2
0
d ln K r H van’t Hoff equation
dT RT 2
For exothermic reactions, K decreases with increasing T
𝜟𝒓 𝑯 𝟎 𝟏 𝟏
𝐥𝐧 𝑲𝟐 𝐥𝐧 𝑲𝟏
𝑹 𝑻𝟐 𝑻𝟏
Gr0 G 0f G 0
f
pdts reactants
aA+bB→cC+dD
If ΔrG o > 0 then the reaction will not go as written (the reverse
reaction will go); if ΔrG o < 0 then the reaction will go as written.
Swagata Dasgupta, Chemistry IIT Kharagpur 11
Le Châtelier’s Principle
“If a system at equilibrium is disturbed by a change in
temperature, pressure, or the concentration of one of the
components, the system will shift its equilibrium position so
as to counteract the effect of the disturbance.”
A change imposed on an equilibrium
system is called a stress
The equilibrium always responds in such
a way so as to counteract the stress
• Change in concentration of one or more reactants or products
• Change in temperature
• Change in pressure
• Addition of a catalyst
Gr 0 Gr0 RT ln K a
Gr0 RT ln K a
Gr 0 Gr0 RT ln K a
Gr0 RT ln K a
G 0
K a exp RT
H 0 TS 0
K a exp RT
H 0 S 0
K a exp RT
exp R
Swagata Dasgupta, Chemistry IIT Kharagpur 12
Equilibrium Constant for non-ideal gases
pCc p Dd Cc Dd
Ka
p Aa p Bb Aa Bb
For solute in solutions
Ideal 𝜇 𝜇 𝑅𝑇 ln 𝑚
Non-ideal 𝜇 𝜇 𝑅𝑇 ln 𝑚 𝛾
Equilibrium constants at other temperatures
Gibbs-Helmholtz equation,
Equation valid for chemical reactions with G 0 RT ln K a
their components in their standard states
Swagata Dasgupta, Chemistry IIT Kharagpur 13
• Relation between Kp & Kc
• The van’t Hoff eqn.; Dependence of equilibrium constant on T
d ln K H r0
d (1 / T ) R
H r0 1 1
ln K 2 ln K1
R T2 T1
• Effect of pressure on Kp, Kc; Le Chatelier’s principle
Response of equilibria to pressure change
𝐴 𝑔 → 2𝐵 𝑔
𝑡 0 1 0
is the degree of dissociation
𝑎𝑡 𝑒𝑞𝑙𝑚 1 𝛼 2𝛼
1 𝛼 2𝛼
𝑥
1 𝛼 1 𝛼
1 𝛼 2𝛼
𝑝 𝑝 𝑝 p is in bar
1 𝛼 1 𝛼
𝑝 4𝛼
𝐾 𝑝
𝑝 1 𝛼
𝜕𝐾
But we know, 0
𝜕𝑝
/
1
𝛼
4𝑝
1 𝐾 Le-Chatelier principle
Swagata Dasgupta, Chemistry IIT Kharagpur 14
Mixing of Ideal Solutions
Gi n A *A nB B*
Gf n A *A RT ln x A nB B* RT ln xB
Gmix nRT xi ln xi
i Ideal solution – Raoult’s law
S mix nR xi ln xi
Leading to ideal solution, similar to mixing of ideal gases.
i
H mix 0 InteractionAB = InteractionAA =InteractionBB
Gmix
Vmix 0 Excess enthalpy
p T (benzene+cyclohexane)
Mixing of Real Solutions (excess functions)
S E Smix Smix (ideal )
Excess entropy
InteractionAB < InteractionAA
InteractionAB < InteractionBB
Prove the following relations:
U T
p 0 (for ideal gas) an2 / V 2 (for vdWgas)
V T
H
V (1 T ) 0 (for idealgas) ? (for vdWgas)
p T
S S S C S Cp
V V
p T V T T V T T p T
JT
V
T 1 ? (for idealgas) ? (for vdWgas) What is
the
Cp relation
between
Cp and CV
TV 2 of water at
C p CV nR (for idealgas) 3.98 0C?
Swagata Dasgupta, Chemistry IIT Kharagpur 15
Variation of entropy with temperature at constant p or constant V
dU pdV TdS dH VdP TdS
U S H S
T T
T V T V T p T p
S S
CV T Cp T
T V T p
S C S Cp
V
V T
T
p T
T
Variation of entropy with temperature and pressure
S S S V
dS dT dp V
T p p T
T
p T p
Cp From Maxwell relation
dS dT Vdp
C
S P dT VdP
T
T
Dependence of state functions (U, H, and S) on T, p, and V
U U U U T
dU dT dV CV p
T V V T T V V T
T
U CV dT
p dV
H H H H
dH dT dp Cp V (1 T )
T p p T T p p T
H C pdT (V TV )dp
S S S Cp S
dS dT dp V
T p p T
p T
T
p T
T dT VdP
CP
S
Swagata Dasgupta, Chemistry IIT Kharagpur 16