Course outline

Physical Chemistry
• Essential concepts and definitions in
Thermodynamics
• Revision: heat, work & energy; Real gas
• First Law of Thermodynamics
• The Second Law of Thermodynamics
• Entropy
• Gibbs Free Energy
• The Chemical Potential
• Phase and Reaction Equilibria
• Chemical Kinetics
CY11001 Sec13&14 (spring 16) Department of Chemistry
 Thermodynamics

• The study of the transformations of energy (work, heat,

energy and their effect on the state of the system).
Concerned with equilibrium positions of systems.

• Provides a framework of relating the macroscopic

properties of a system to one another.

• Our discussions will be restricted to equilibrium

thermodynamics which deals with systems in equilibrium.

CY11001 Sec13&14 (spring 16) Department of Chemistry

 SOME BASIC CONCEPTS:

 Thermodynamic System – Open, Closed, Isolated

 Surroundings

 Boundary / Wall
• Rigid and Nonrigid (movable)
• Permeable and Impermeable
(no matter is allowed to pass through it)
• Adiabatic and Nonadiabatic
(diathermic boundary –
permits the passage of energy as heat )

A system surrounded by a rigid,

impermeable, adiabatic wall –
Isolated system
CY11001 Sec13&14 (spring 16) Department of Chemistry
Thermodynamic Equilibrium
For Isolated system:
Macroscopic properties do not change with time

For Non-isolated system:

a) Macroscopic properties do not change with time
b) Removal of the system from contact with its
surroundings causes no change in the properties of
the system

• Mechanical Equilibrium
• Thermal Equilibrium
• Material Equilibrium

CY11001 Sec13&14 (spring 16) Department of Chemistry

Mechanical equilibrium

the condition of equality of

pressure on either side of a
movable wall.
No unbalanced forces act on or
within the system – system does
not undergo acceleration or no
turbulence inside the system

CY11001 Sec13&14 (spring 16) Department of Chemistry

 Thermal equilibrium
between system and the
surroundings, is a condition in which
no change in the properties of the
system or surroundings when they are
separated by a thermally conducting
wall.

CY11001 Sec13&14 (spring 16) Department of Chemistry

Material equilibrium
Concentrations of the chemical species in the various
parts of the system are constant with time

a) No net chemical reactions are occurring in the system

b) There is no net transfer of matter from one part (phase)
of the system to another or between the system and its
surroundings

For thermodynamic equilibrium, all three kinds of

equilibrium must be present

CY11001 Sec13&14 (spring 16) Department of Chemistry

 Thermodynamic Properties:

Intensive properties (do not depend on the size of

the system, density, pressure)

Extensive properties (they do. Ex: mass, volume)

If each intensive property is constant throughout the

system,

Homogeneous system

Heterogeneous system
a homogeneous part of a system is called a
phase
CY11001 Sec13&14 (spring 16) Department of Chemistry
 How do we define a system? State of a System
Macroscopic state of a system can be specified by the values
of a small number of macroscopic
Properties/Parameters/Physical characteristics or attributes of
a system - Thermodynamic variables
Thermodynamic variables which are experimentally
measurable
• Composition – mass of each chemical species that is present in
each phase,
• pressure (p or P), volume (V), Temperature (T), density, etc.
• field strength, if magnetic/electrical field act on the system
• gravitational field
If the value of every thermodynamic property in system A is
same as in system B – same thermodynamic state

Microscopic state of a system needs description about

each molecules – a very complicated picture
CY11001 Sec13&14 (spring 16) Department of Chemistry
 Essential concepts / Definitions

Thermodynamic Processes:
When one or more of the thermodynamic properties of a system changes, the
state of the system also changes and system is undergoing a process

Isothermal (constant T),

Isobaric (constant p),
Isochoric (constant V)
Adiabatic
Exothermic & Endothermic
Cyclic
Reversible & Irreversible

CY11001 Sec13&14 (spring 16) Department of Chemistry

 Essential concepts / Definitions
Reversible process:
• Ideal
• Change must occur in successive stages of infinitesimal
• quantities
Infinite duration
Virtual thermodynamic equilibrium, at each of the small stages.
 Backward changes of the thermodynamic quantities in different
stages will be the same as in the forward direction but
opposite in sign with respect to the forward direction

Irreversible Process:
· Real / Spontaneous
· Occurs suddenly or spontaneously without the restriction of
occurring in successive stages of infinitesimal quantities.
 Does not remain in the virtual equilibrium during the transition.
 The work in the forward and backward processes can be
unequal.

CY11001 Sec13&14 (spring 16) Department of Chemistry

 Zeroth Law of Thermodynamics –
Temperature (Flower, 1931)

Temperature is a property associated

with random motion of many
particles.
Introduction of the concept of
temperature in thermodynamics is based
on the the zeroth law of
thermodynamics:
A well-defined quantity called
temperature exists such that two
systems will be in thermal equilibrium if
and only if both have the same
temperature.
Application of Zeroth Law of Thermometer
Thermodynamics:
CY11001 Sec13&14 (spring 16) Department of Chemistry
 The Equation of State
An equation that relates macroscopic variables (e.g., p, V, and T) for a
given substance in thermodynamic equilibrium.

p = f (V,T,n)

• Equation of state is not a theoretical deduction from thermodynamics,

rather an experimental addition to it. An equation of state is as
accurate as the experiments that led to its formulation. It holds only
within the range of measurement.
perfect/ideal gas equation, pV =
nRT.

perfect/ideal gas, a gas that obeys pV =

nRT exactly under all conditions.

gas constant, R (with R = NAk, where NA is

Avogadro’s constant and k is Boltzmann’s
constant).

CY11001 Sec13&14 (spring 16) Department of Chemistry

 The Equation of State (Ideal Gas)

Surface of possible states

CY11001 Sec13&14 (spring 16) Department of Chemistry

Mixture of Gases

 Partial pressure: of a gas (i), in a mixture of any gases

pi = xi p, xi=Mole fraction of the component.

 Dalton’s law: The pressure exerted by a mixture of (ideal)
gases is the sum of the partial pressures that each one would
exert if it occupied the container alone.
p  pi .
i

 vapour pressure, the pressure of a vapour in equilibrium

with its condensed phase.

CY11001 Sec13&14 (spring 16) Department of Chemistry

 Deviation from ideality: REAL GAS
Compression/compressbility factor:
Z (p,T)= Vm/Vm
Z(p, T) = pVm / RT
• At very low pressure and high temp.;
Z ~ 1 (Perfect gas behavior)

• At high p, molecular volume

significant, repulsion dominates
Vm > Vm,ideal  Z > 1

• At intermediate p, (& low temp),

insignificant molecular volume;
attraction dominates
Vm < Vm,ideal  Z < 1

CY11001 Sec13&14 (spring 16) Department of Chemistry

 The Equation of State for Real Gases

Virial Equation of State

At very low pressure, real gases behave ideally.

Hence, let the ideal gas law be the first term in a
series in powers of a variable (p or 1/Vm)

pVm= RT (1 + B’ p + C’ p2 … )

pVm= RT (1 + B/Vm + C/Vm2 … )

B’ and C’ are 2nd and 3rd virial coefficients (at temp

T)

As, p  0, virial equation reproduces ideal gas

equation.

Z = (1 + B’ p + C’ p2 ) = (1 + B/Vm + C/Vm2 )

The properties of real gases do not always

coincide with the perfect gas values at low
pressures.
CY11001 Sec13&14 (spring 16) Department of Chemistry
Condensation of a real gas
Critical Constants (Tc ; pc ; Vc):

Temperature at and above which the

separation of liquid and gas surface
ceases to exist.
At the critical point,
dp d2p
0 and 2
0
dVm dVm
Tc: Highest T at which condensation of
a gas is possible.

pc : Highest p at which a liquid boils

when heated.

CY11001 Sec13&14 (spring 16) Department of Chemistry

 The Principle of Corresponding States

Real gases at same reduced volume

and reduced temperature exert
same reduced pressure and have
same compressibility factor.

Reduced Variables:

Vr=Vm/Vc
Tr=T/Tc
pr=p/pc

Limitations:
Polar or non-spherical molecules.
CY11001 Sec13&14 (spring 16) Department of Chemistry
 The van der Waals model of real
gases

Veff V  nb p
nRT
(Ideal gas equation)
repulsion V

nRT an 2  an 2 
p   p  2  V  nb  nRT
V  nb V2  V 
attraction
The van der Waals equation of state for real gases

 At high temperature and large volume, vdW equation reduces

to ideal gas law.
 Liquid and gases coexist when attractive and repulsive forces
balance

 Critical Constants and vdW parameters: Vc=3b, pc=a/27b2,

2
Tc=8a/27Rb, Zc=pdp V /RT =3/8
c c 0cand
d p critical compression factor)
(the0
dVm 2
dVm
CY11001 Sec13&14 (spring 16) Department of Chemistry
 The First Law of Thermodynamics:

• There exists an extensive state function E such that for

any closed system, E = q + w
• In absence of any external field acting on the system and
the system at rest, E = U (K=V=0)
· w, work done on the system
U = q + by the surroundings
w
· q, heat absorbed by the
dU = dq+dw = dq + dw = dq + dw
system from the surroundings
· The conventions for the signs of
q and w are set from the
system’s perspective
• For isolated system, dU = 0
• For adiabatic process, q=0; dU = w


• For cyclic process,dU 0; q -w

CY11001 Sec13&14 (spring 16) Department of Chemistry

Energy
E=K+V+U
• K and V are the macroscopic (not molecular) kinetic
and potential energies of the body, together represent
the mechanical energy
• U is the internal energy of the body (due to molecular
motions and intermolecular interactions)

Internal Energy, U, is the total energy within a system. (E=U,

as K=V=0 )
• Extensive property
• Um=U/n (molar internal energy)
• It is a state function, independent of path
• dU is a perfect (exact) differential
• For cyclic processdU 0

CY11001 Sec13&14 (spring 16) Department of Chemistry

olecular Interpretation of Internal Energy:
U m U tr , m  U rot , m  U vib, m  U el , m  U intermol, m

3 U vib , m  0 for monoatomic

U tr , m  f(T)  RT
2 U vib , m  f (T )

Small in magnitude and nearly

constant for diatomic and light
U rot , m  0 (monoatomic) molecules at low to moderate
temperature.
U rot , m  RT (linear molecules)

U rot , m 
3
RT (nonlinear molecules) For Ideal Gas
2 3
U m  RT  const. (monoatomic)
2
U intermol, m  f(T,p ( orV))
U m  RT  RT (or RT )  U vib, m T  const.
3 3
2 2
 0 (for ideal gas)

• Internal energy of ideal gas increases

U el , m  constant if temp is not
linearly with T
extremely high and no chemical reaction
• Internal energy of ideal gas is independent
Heat

• Heat is that which is transferred between a system

and surrounding by virtue of a temperature difference
only.

• Heat is not a state function (path dependent).

• Heat can be transferred reversibly or irreversibly. A

reversible transfer of heat requires the temperature
difference between two bodies be infinitesimal.

CY11001 Sec13&14 (spring 16) Department of Chemistry

 Work:
• expansion work, work of expansion (or compression)
• non-expansion / additional work: any other work

Expansion Work:
General expression of work (reversible process):
pex = external pressure
A = piston area
dz = displacement
dV = A dz =volume change for the gas

Work is required to move an object a distance dz

against an opposing force F. Total work done,
Vf Vf

w  F dz  ( pex A)dz  p ex dV  pdV Only for reversible process

Vi Vi

dV change in the volume of the system

CY11001 Sec13&14 (spring 16) Department of Chemistry
 Chemical example: expansion of a gas
pansion against constant pressure
formed in a chemical reaction in a
container that can expand

Vf
Indicator diagram or pV diagram
w  p
Vi
ex dV  pex (V f  Vi )  pex V

pansion against constant final pressure:

w  p f (V f  Vi )

Free expansion:
Expansion against zero opposing force
w=0

Expansion, i.e., Vf > Vi , w < 0 (work done by

the system on surrounding)
Compression, i.e., Vf < Vi , w > 0 (work done
on the system by surrounding)
CY11001 Sec13&14 (spring 16) Department of Chemistry
 Isothermal expansion (ideal gas):
Reversible

Vf
Vf dV Vf
w   pdV  nRT   nRT ln
Vi
Vi
V Vi

• At higher T, work done is more for same

expansion of volume.

Work against constant final pressure

Irreversible w  p f (V f  Vi )  p f V

|wrev| > |wirrev| Maximum work is obtained when

expansion is reversible.
CY11001 Sec13&14 (spring 16) Department of Chemistry
diabatic Reversible Process for ideal gas, (CV independent of Temp)

dU dw  dq dw

For ideal gas,CV dT  pdV

T2 dT V2 dV
CV
 T1 T
- nR
 V1 V
T2 V
CV ln nR ln 1
T1 V2
CV nR C p  CV
 T2  V  V 
   1   1 
 T1   V2   V2 
 1
T2  V1  C p ,m
  where  
T1  V2  CV ,m
PV  constant
TV   1 constant VT c constant
T  P1  constant
CY11001 Sec13&14 (spring 16) Department of Chemistry
|wrev (compression)| = |wrev(expansion)|
Work is path dependent:

al gas, closed system, reversible process

Calculate wf and wb

wrev depends on the path used to go from 1

to 2, and wrev can have any positive or
negative value for a given change of state

Homework
 Work
w 
pex dV  pex V
Irreversible

Reversible
0 (at 0 p, free expansion)

w
ge
) pV
n
c ha
s e
w 0(erev, at c n
p
t ng; pha
x: a
bo onst
mb n st eati
a o
cal nt V a tc tph
ori , ns
em rev : co
ete
r) (ex
vdW gas, rev
w 
 nRT

 
an 2
 V  nb V 2

 dV
 s,
rev w  p dV
 Id
Ideal gas, rev
Is eal w 
nRT
 dV
  ga al ot g V
W rm he as
vd the rm
iso al
V2  nb  1 1  re
w  nRT ln  an 2   

ve
V1  nb V
 1 V 2 adiabatic reversible rs
ib
le Vf
w  nRT ln
Vi
w 
pdV C V dT

CY11001 Sec13&14 (spring 16) Department of Chemistry

Heat Transactions and Heat Capacity:
In general change in the internal energy
of a closed system is given by
dU dq  dwexp  dwadd
• For dV = 0; dwexp = 0 and if dwadd = 0, then
The measurement
dU = dq
(constant volume, no additional work)
= dqV of internal energy
change
For a measurable change U = qV • Adiabatic bomb
calorimeter
- heat capacity, C, the ratio of the heat supplied
to the
temperature rise it causes. C = dq/dT; C = q/ T
- heat capacity at constant volume, CV =
- molar heat capacity, the heat capacity divided
( U/ T)V
by the
amount of substance, Cm = C/n.
- specific heat capacity, the heat capacity
divided by
the mass, Cs 16)
CY11001 Sec13&14 (spring
= C/m Department of Chemistry
 eat Capacity at Constant Pressure:
dU dq  dwexp  dwadd

For dV ≠ 0; dwexp ≠ 0 Even if dwadd = 0, dU ≠ dq

Define H = U + pV
H = dU + pdV + Vdp = dU – w (at const p) = dqp

at capacity at constant pressure, Cp = ( H/ T)p

mpirical expression, Cp,m = a + bT + c/T2
The measurement of enthalpic
For ideal gas; relation between ΔU change
• isobaric calorimeter
and ΔH, • differential scanning calorimeter
ΔH = ΔU + ΔngRT. • adiabatic flame calorimeter
Show that for a perfect gas, Cp – CV
• For most cases, Cp > CV
= nR
(home work)
CY11001 Sec13&14 (spring 16) Department of Chemistry
Partial differentiation:
Consider a function of two variables  z = f(x,y)
A partial derivative of one of the
variables: the rate of change of the function
wrt that variable with all other variables
kept fixed.

Example: For z = f(x,y),

 z  f ( x  x, y )  f ( x, y )  z  f ( x, y  y )  f ( x, y )
   lim    lim
 x  y x 0 x  y  x y  0 y

Total differential of z(x,y):

 z   z 
dz   dx    dy
 x  y  y  x

2 z  2 z Clairaut’s  y   z   x  Cyclic
   .  .   1
Rule
xy yx theorem  z  x  x  y  y  z

CY11001 Sec13&14 (spring 16) Department of Chemistry

Partial derivatives of p, Vm, and T with respect to each
other:
Vm = f(p,T); p = f(Vm,T); T = f(p,Vm)

 T   T 
dT   dp    dVm  p   Vm   T 
 p  Vm  Vm  p        1
 Vm  T  T  p  p  Vm
 p   p 
dp   dT    dVm
 T  Vm  Vm  T  2T  2T  1 
   for ideal gas 
 V   V  pVm Vmp  R 
dV m m  dT   m  dp
 T  p  p T
• How fast the
1  Vm  1  Vm  (fraction of)
 (T , p )     (T , p )    
Vm  T  p Vm  p  T volume increases
with temperature
Expansion coefficient Isothermal compressibility and decreases
with pressure
 p  Vm / T p  (T , p )
    • For ideal gas, a=
 T  Vm Vm / p T  (T , p ) 1/T and k= 1/p

CY11001 Sec13&14 (spring 16) Department of Chemistry

 Limitations of the First Law of
Thermodynamics
The first law assures us that the total energy of system
plus surroundings remains constant during the reaction.
Energy can be transferred/transformed, keeping the total
energy fixed.

dUuniverse = dUsystem + dUsurrounding = 0

Does not say:

Whether energy will get transferred / transformed?
If yes, in which direction?
If yes, how long?
If yes, how fast?

CY11001 Sec13&14 (spring 16) Department of Chemistry

 In all the cases first law allows either
outcomes, but we observe only one
outcome spontaneously.

CY11001 Sec13&14 (spring 16) Department of Chemistry

 Spontaneity:

A spontaneous process occurs naturally and needs no

external source of work. A non-spontaneous process,
although allowed by first law of TD, requires an external
source of work to drive it.

Who drives, a spontaneous process?

CY11001 Sec13&14 (spring 16) Department of Chemistry

 Entropy
• The thermodynamic property of a system that is related
to its degree of randomness or disorder is called entropy
(S).
• The entropy S and the entropy change ΔS = S2 -
S1 are state functions.

• The entropy S has a unique value, once the pressure

p, the temperature T and the composition n of the
system are specified, S=S(p,T,n).

• The entropy is an extensive property, i.e., increases

with the amount of matter in the system. Sm= S/n (molar
entropy).

CY11001 Sec13&14 (spring 16) Department of Chemistry

ermodynamic definition of entropy

dSsyst = Change in entropy that occurs during a

chemical or physical process

= dqrev / T (qrev is the heat supplied surrounding system

reversibly) 2
dqrev
S system 
1
T

For surroundings,
Large change in
dSsurr = - dq/Tsurr
entropy occurs when
heat is dissipated to
 q
S surr  surrounding at low
Tsurr temperature.

CY11001 Sec13&14 (spring 16) Department of Chemistry

w do you calculate entropy change?
For surrounding
surrounding system

dSsurr = - dq / Tsurr
 q
S surr 
Tsurr
Calculate the actual q for the process from state 1 to state 2 and
apply the above formula

For system
• Find out state 1 and state 2
• Construct reversible pathway(s) from state 1 and state 2
• Apply the formula 2
dq
S  rev
1
T

• Calculate the entropy change in the surroundings when 1.0 mole

of H2O(l) is formed from its elements under standard conditions at
25° C (298.15 K). H2(g) + 1/2 O2(g) = H2O (l) DfH= -286 kJ/mol.
CY11001 Sec13&14 (spring 16) Department of Chemistry
ulation of Entropy Changes (A few special cases) 2
dqrev
S system 
1. Cyclic ProcessDSsyst= 0 (S is a state function) T
1
DSsyst= 0 (dqrev=0)
2. Reversible adiabatic process
3. Reversible phase-change at constant p and T
2 dq 2
rev 1 q rev H
S syst    dq
rev
 
1
T T
1
T T
4. Constant p heating (reversibly) with no phase change:
T T
dq rev dq p C p dT 2 dq
rev  C
2 dT  T2 
  C ln  
p T
S syst 
T p T
T T  1 
1 1
5. Reversible isothermal process:
2 dq 2 q rev
rev 1
S syst    dq 
T T rev T
1 1
6. For ideal gas: dq dU  w CV dT  pdV dT dV
rev rev
dS    CV  nR
T T T T V
T V T2 p1
S CV ln 2  nR ln 2 S C p ln  nR ln
T1 V1 T1 p2
CY11001 Sec13&14 (spring 16) Department of Chemistry
lculation of Entropy at any temperature
Heating at constant pressure/Volume
Cp T2
S p 
 T
dT C p ln
T1
CV T2
SV 
 T
dT CV ln
T1

Entropy at any temperature,

Tf Tb T
C p (s ) H fus C p (l) H vap C p (g )
S (T ) S (0)   dT   dT   dT
0
T Tfus Tf
T Tvap Tb
T

Debye Extrapolation: At low T, Cp  T3

Trouton’s Rule
A wide range of liquid give approx. the same
standard entropy of vaporization ~ 85 J K-1 mol-
1
. Exception: water, it is 109 J/K/mol
CY11001 Sec13&14 (spring 16) Department of Chemistry
ruction of Reversible Steps to Describe an Irreversible Pro

Example 1:

Liquid Water at Irreversible DS =? Ice at -10 0C, 1

-10 0C, 1 atm DS = DS1 + DS2 + DS3 atm

Reversible
Reversible
heating at
cooling at
constant
constant
pressure, DS1
pressure, DS3

Reversible phase
Liquid Water at change at Ice at 0 0C, 1
0 0C, 1 atm constant atm
Temperature and
pressure, DS2

Entropy is an extensive property. DS = DS1 + DS2 + DS3

ruction of Reversible Steps to Describe an Irreversible Pro
xample 2: Entropy of Mixing of ideal gases
p, T, V1, n1 p, T, V2, n2
S mix S1  S 2
Irreversible
mixing of gases
DS=?
p, T, V1 +V2, n1
+ n2
p, T, V1, n1 p, T, V2, n2

Reversible,
isothermal
expansion
T, V1 +V2, n2
T, V1 +V2, n1
V1  V2 V1  V2
S1 n1 R ln S 2 n2 R ln
V1 V2
ruction of Reversible Steps to Describe an Irreversible Pro
ample 2: Entropy of Mixing of ideal gases
p, T, V1, n1 p, T, V2, n2

Irreversible
mixing of gases
S mix S1  S 2
p, T, V1 +V2, n1
+ n2 V1  V2 V1  V2
S1 n1R ln , S 2 n2 R ln
V1 V2
n1RT
V1 p n1
   X1
V1  V2 n1RT n2 RT n1  n2

*Find out X1 for p p
which DSmix is S mix  n1R ln X1  n2 R ln X 2
maximum.  nR ( X1 ln X1  X 2 ln X 2 )
tatistical View of Entropy
The equilibrium thermodynamic state of an isolated
system is the most probable state.

S k B ln W
kB is Boltzmann’s constant
W is number of different ways in which the energy
of the system can be arranged (number of
microstates)

W = 21 X 20 X 19 = 7,980 W = 63 X 62 X 61 = 2,38,266
CY11001 Sec13&14 (spring 16) Department of Chemistry
The Clausius Inequality:
2
dqrev S  q
dS = dqrev / T S  surr 
T Tsurr
dSsurr = - dq / Tsurr 1

|dwrev |> |dw|

- dwrev > - dw For a closed system,

dw - dwrev  0
dq = dU - dw
Since dU = dq + dw = dqrev + dwrev TdS  dU – dw
dU - TdS - dw ≤ 0
dqrev  dq
dqrev /T  dq/T
Entropy can not decrease
when a spontaneous change
dS  dq/T The Clausius occurs in an isolated system
Inequality (dq = 0)
CY11001 Sec13&14 (spring 16) Department of Chemistry
Entropy and Reversibility
• Reversible process:

Reversible heat transfer between system and surrounding must

occur with no finite temperature difference.
dqrev dq
Tsyst Tsurr  dSuniv dS syst  dS surr   0
Tsyst Tsurr

• Irreversible process (spontaneous):

The system + surrounding = universe, can be considered an

isolated system. For any isolated system, dSuniv = dSsyst + dSsurr
>0

Suniv 0

CY11001 Sec13&14 (spring 16) Department of Chemistry

Entropy and Equilibrium
• For an isolated system, spontaneous changes will occur until
the entropy is maximized. This leads to equilibrium.

• For a closed system (heat and work exchange with

surrounding is allowed), spontaneous changes will occur until
the entropy of system plus surrounding, is maximized. This
leads to equilibrium.
dStotal = dSsys + dSsurr > 0 Spontaneous process
dStotal = dSsys + dSsurr = 0 Equilibrium process
dStotal = dSsys + dSsurr < 0 Impossible process

For any process

“=“ for reversible, equilibrium
dSsys + dSsurr  0 “>” spontaneous (irreversible) (real)

CY11001 Sec13&14 (spring 16) Department of Chemistry

 dq
dS  (Clausius Inequality)
T

TdS  dq 0
TdS  dU  dw 0
dU  TdS  dw 0

CY11001 Sec13&14 (spring 16) Department of Chemistry

onditions for Spontaneity
For a closed system dU - TdS – dwpV – dwnon pV ≤ Condition for spontaneity

0 V
Const. Const. T
dwpV = 0 A = U - TS

dU - TdS - dwnon pV ≤ 0 dA- dw tot ≤ 0

for dwnon pV = 0 dA ≤ dwtot

dU - TdS ≤ 0 dUS, V, no non pV work ≤ 0 (- dA) ≥ (- dwtot)

Const. T dSU, V, ≥ 0
no non pV work
d(U-TS) ≤ 0
Helmholtz’s energy /
A = U - TS Helmholtz’s free energy /
Helmholtz’s function/ (- dA) = (- dwtot ) max
dAV, T, no non pV work ≤ 0 Maximum Work Function

For a closed system at constant T and V, the state function A = U-TS decreases
during the spontaneous irreversible process
CY11001 Sec13&14 (spring 16) Department of Chemistry
onditions for Spontaneity
For a closed system dU - TdS + pdV – dwnon pV Condition for spontaneity

≤ 0
Const. p, dH = dU + pdV + Vdp

dH - TdS - dwnon pV ≤ 0 dH - TdS - dwnon pV ≤ 0

for dwnon pV = 0
Const. T
dH - TdS ≤ 0 dHS, p, ≤ 0
no non pV work G = H - TS
Const. T dSH, p, ≥ 0
no non pV work

d(H-TS) ≤ 0
- dGp,T ≥ (- dwnon pV)
G = H - TS Gibbs’s energy /
Gibbs’s free energy /
dGp, T, no non pV work ≤ 0 Gibbs’s function
- dGp, T = (- dwnon pV) max
At constant temperature and pressure, chemical reactions are spontaneous in the
direction of decreasing Gibbs energy.
CY11001 Sec13&14 (spring 16) Department of Chemistry
Criteria for spontaneity
dSsys + dSsurr > 0
For a closed system, no non p-V (additional) work

dUS,V ≤ 0 dHS,p ≤ 0 dAV,T ≤ 0 Reversible processes

dSU,V  0 dSH,p  0 carry equal sign.
dGp,T ≤ 0

CY11001 Sec13&14 (spring 16) Department of Chemistry

 dq
2
 q
S  rev S surr  Thermodynamic definition of entropy
1
T Tsurr

Entropy is a state function.

dS 0 Change in entropy for a cyclic
process is zero.
dS  The Clausius inequality relation.
dq/T 2nd law of thermodynamics. Total
dSsys + dSsurr  0 entropy increases for
spontaneous processes.
Helmholtz free energy
A = U – TS (- dA)T,V = (- dwtot) max corresponds to total work
function (at const T and V) and
G = H - TS - dGp, T = (- dwnon pV) max Gibbs free energy corresponds to
total non-pV work (at constant p
and T).
dUS,V ≤ 0 dHS,p ≤ 0 dAV,T ≤ 0 Spontaneity of processes. Equality
holds good for reversible processes
dSU,V  0 dSH,p  0 dGp,T ≤ 0 or system in equilibrium.
mbination of First and Second Laws of Thermodynamics:

dU = dw + dq True for any path dU = dwrev + dqrev

dS  dq/T dS = dqrev/T

The Fundamental
Equation of
dU = - pdV + TdS Thermodynamics

dA d (U  TS ) Applicable to both
dU  TdS  SdT reversible and irreversible
processes!
 pdV  TdS  TdS  SdT
 pdV  SdT

dH TdS  Vdp
dG Vdp  SdT
The Fundamental Equation of Chemical
CY11001 Sec13&14 (spring 16)
Thermodynamics
Department of Chemistry
mbination of First and Second Laws of Thermodynamics:
e Gibbs Equations)

dU  pdV  TdS
dA  pdV  SdT
dH TdS  Vdp
dG Vdp  SdT

A closed system (constant composition/change in

composition reversibly), only pV work

CY11001 Sec13&14 (spring 16) Department of Chemistry

 The Maxwell Relations if, df  gdx  hdy
 g   h 
then    
 y  x  x  y
 S   V  The Euler Reciprocity
dG Vdp  SdT  
p
 
 T

p Relation.
 T
Isothermal
variation of entropy
 S   p  with pressure and
dA  pdV  SdT     volume
 V  T  T  V

 T   p 
dU  pdV  TdS     
 V S  S V

 T   V 
dH Vdp  TdS    
 p S  S p

CY11001 Sec13&14 (spring 16) Department of Chemistry

ariation of Gibbs free energy with T and p

dG Vdp  SdT  G   G 
   S   V
The Fundamental Equation  T  p  p  T
of Chemical
Thermodynamics

p2
Gm 
V dp
p1
m

RT ln( p2 / p1 )

Gm Vm p

CY11001 Sec13&14 (spring 16) Department of Chemistry

Temperature dependence of Gibbs
Energy
Or Gibbs-Helmholtz Equation:
G H  TS
 G 
   S (G  H ) / T
 T  p
  (G / T )    (G / T ) 
  ?   ?
 T  p   (1 / T ) p

Show that (home work)

  (G / T )  H   (G / T ) 
   2   H
 T  p T   (1 / T )  p If we know DH of
a process, we can
  (G / T )  H   (G / T )  know how DG/T
     H
T T2 varies with T.
 p   (1 / T )  p
Gibbs-Helmholtz Show that, DG/T = -DSuniv
Equations

CY11001 Sec13&14 (spring 16) Department of Chemistry

ove the following relations:
 U   T 
    p  0 (for ideal gas) an 2 / V 2 (for vdW gas)
 V T   

 H 
  V (1  T ) 0 (for ideal gas) ? (for vdW gas)
 p T

 S   S    S  CV  S  Cp
   V         
 p T  V  T   T V T  T  p T

V
 JT  T  1 ? (for ideal gas) ? (for vdW gas) What is
the
Cp relation
between
Cp and CV
TV 2 of water
C p  CV  nR (for ideal gas) at 3.98
 0
C?
CY11001 Sec13&14 (spring 16) Department of Chemistry
ion of entropy with temperature at constant p or constant
dU  pdV  TdS dH VdP  TdS
 U   S   H   S 
  T     T  
 T V  T V  T  p  T  p

 S   S 
CV T   C p T  
 T V  T  p

 S  C  S  Cp
   V   
 T V T
 T  p T

riation of entropy with temperature and pressure

 S   S   S   V 
dS   dT    dp       V
 T p  p T p
 T  T p
Cp
dS  dT  Vdp From Maxwell relation
T CP
S  dT  VdP
T
CY11001 Sec13&14 (spring 16) Department of Chemistry
ndence of state functions (U, H, and S) on T, p, and V
 U 
dU 
 U   U   U   T 
 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 C p     V (1  T )
 T  p  p  T  T p  p T

 
H  C p dT  (V  TV )dp

 S   S   S  Cp  S 
dS   dT    dp       V
 T  p  p T  T  p T  p T

CP
S 
T 
dT 
VdP
CY11001 Sec13&14 (spring 16) Department of Chemistry
Heat Engine
An engine is a device (system) that converts energy
to work.

A heat engine draws heat from a hot reservoir,

converts some heat to work, and releases some heat
to a cold reservoir.

The engine itself is a system that undergoes a cyclical

process
Experiments suggested:

(Clausius) An engine does not exist whose sole

effect is to transfer heat from a cold body to a
hot body.
(Kelvin) An engine does not exist that operates
in a
cycle and performs work by exchanging heat
with only one reservoir!

CY11001 Sec13&14 (spring 16) Department of Chemistry

Carnot Engine (1825, Sadi Carnot)
TV   1 const.;
 1  1
ThVB TCVC
 1  1
ThVA TCVD
 1  1
 VB  V   VB  V 
   C     C 
 VA   VD   VA   VD 
ln (VD / VC )  ln (VB / VA )

1 (A to B) 2 (B to C) 3 (C to D) 4 (D to A) Total (A to A)

w -nRTh ln(VB/VA) CV (Tc-Th) -nRTc ln(VD/VC) CV (Th-Tc) -nR(Th-Tc) ln(VB/VA)

q nRTh ln(VB/VA) nRTc ln(VD/VC) 0 nR(Th-Tc) ln(VB/VA)

0
DU
0 CV (Tc-Th) 0 CV (Th-Tc) 0

0 nR ln(VD/VC) 0 0
(qrev/ T) nR ln(VB/VA)
Efficiency of Carnot cycle
work performed

heat absorbed from source
 w nR (Th  Tc ) ln(VB / V A )
  tot 
q nRTh ln(VB / V A )
Th  Tc Tc
 1  1
Th Th
Tc qc
 1  1 
Th qh
All reversible engines have same efficiency
regardless of their construction

he total change in entropy during a Carnot cycle:

q h qc
dS  
Th Tc
0 Entropy change around any closed path is 0
Entropy is a state function.
 Thermochemistry

plication of Thermodynamics to Chemistry - Thermochemis

• Make a cold drink (put ice to water!)

• Burn fuel to drive a car
• Burn fat by doing exercise
• Hot packs and cold packs
• Equipment cooling

2C57 H110 O6 (s)  163O2 (g)  114CO 2 (g)  110H 2O(l)

The decrease in volume at 25 °C is about 600 ml for the consumption of

1 g of fat!
plication of Thermodynamics to Chemistry - Thermochemis
A chemical reaction involves transfer of heat and exchange of energy
between system (reaction vessel) and surrounding. Hence the laws of
thermodynamics are applicable to chemical reactions.
DH > 0 (endothermic); DH < 0 (exothermic);

Enthalpies During Physical Changes

A physical change is accompanied by a standard enthalpy of transition DtrsH0
H 2O (s)  H 2O (l)  fus H 0
H 2O (l)  H 2O (g)  vap H 0

H 2O (s)  H 2O (g)  sub H 0  fus H 0   vap H 0

 trs H 0 ( A  B )   trs H 0 ( B  A)

Standard States: Enthalpy is a state function

For Solid and Liquid – pure form at 1 bar pressure and at the temperature of interest (T).
For gas – pure form at 1 bar pressure and temperature of interest (T) and the gas
behaves as an ideal gas.
Conventionally, the thermodynamic data are reported for standard states at 298.15 K.
CY11001 Sec13&14 (spring 16) Department of Chemistry
xamples of various enthalpies of transition

Enthalpy of vaporization of water is 44 kJ/mol at 298 K. What is the

enthalpy of condensation of water vapor at the same temperature?

CY11001 Sec13&14 (spring 16) Department of Chemistry

Enthalpies During Chemical Changes

aA  bB  cC  dD The standard enthalpy

change,
The change in standard
r H 0  
products
H m0   H m0
reactants
enthalpy during a chemical
reaction is the change in
0
cH m 0
(C )  dH m 0
( D )  aH m 0
( A)  bH m ( B) enthalpy when reactants in
their standard states change
to products in their standard
states.

CH 4 (g)  2O 2 (g )  CO 2 (g)  2H 2O(l )

 r H 0 2 H m
0 0
(H 2O(l))  H m 0
(CO 2 (g))  H m 0
(CH 4 (g))  2 H m (O 2 (g))

For the combustion of methane, the standard reaction enthalpy refers to

the reaction where 1 mol of pure methane gas at 1 bar reacts with 2 mol of
pure oxygen gas at 1 bar to form 1 mol of pure CO2 gas at 1 bar and 2 mol
of pure liquid water at 1 bar.

CY11001 Sec13&14 (spring 16) Department of Chemistry

 C(s)  2 H 2 (g)  CH 4 (g)  r H 0 ?
C(s)  O 2 (g)  CO 2 (g)  r H10
Rxn (1) + 2 Rxn (2) – Rxn(3)
H 2 (g)  1 2 O 2 (g)  H 2O(l)  r H 20
 r H 0   r H10  2 r H 20   r H 30
CH 4 (g)  2 O 2 (g)  CO 2 (g)  2H 2O(l)  r H 30

Hess’s law

The standard enthalpy of an overall reaction is the

sum of the standard enthalpies of the individual
reactions into which a reaction may be divided.
Germain Hess

 r H10  r H 20   r H 30
 r H 40   r H 50   r H 60

CY11001 Sec13&14 (spring 16) Department of Chemistry

tandard Enthalpies of Formation (DfH0)
The standard reaction enthalpy for the formation of the compound
from its elements in their reference state (the most stable state at 1
bar pressure and the specified temperature).
For example –
At 298 K, the reference state of
N2 - N2 gas at 1 bar, Mercury - liquid Mercury at 1 bar,
Carbon - graphite at 1 bar.
fH0 (kJ/mol) at
298 K
Standard enthalpy of formation of H 2CO(g) at
307 K: H2O(l) -285.8
C(s,307 K, 1 bar)  H 2 (g, 307K, 1 bar)  1/2O 2 (g, 307 K, 1 bar) H2O(g) -241.8
 H 2CO(g, 307 K, 1 bar)
NH3(g) -46.1
NO2(g) +33.2
All elements in their reference states
(oxygen gas, solid carbon in the form of C6H6(l) +49.0
graphite, etc.) have a standard enthalpy of
CH4(g) -74.8
formation of zero, as there is no change
involved in their formation. CO2(g) -393.5

CY11001 Sec13&14 (spring 16) Department of Chemistry

alpy of Reaction from Standard Enthalpies of Formation (D
aA  bB  cC  dD

2
3

r H 0  
products
 f H 0    f H 0
reactants
1

CH 4 (g)  2O 2 (g )  CO 2 (g)  2H 2O(l )

 r H 0 2 f H 0 (H 2O(l))   f H 0 (CO 2 (g))   f H 0 (CH 4 (g))  2 f H 0 (O 2 (g))

 r H 0 2( 285.83)  ( 393.5)  ( 74.8)  2(0) kJ/mol  890.36 kJ/mol

CY11001 Sec13&14 (spring 16) Department of Chemistry
Temperature Dependence of DH0
 dH 
  C p
 dT  p
d r H 0
 r C 0p C 0p (product )  C 0p (reactant)
dT
T2


 r H 0 (T2 )   r H 0 (T1 )   r C 0p dT
T1 Kirchhoff’s Law

If DCp does not change over a small temperature range,

 r H 0 (T2 )   r H 0 (T1 )  r C 0p (T2  T1 )

Problem:
Find out DrH0 for the reaction : 2CO (g) + O2(g)  2CO2(g) at 1200 K. Assume DCp is
independent of T.

DfH0 of CO2 (g), and CO(g) at 298 K are -393.5 and -110.5 kJ/mol, respectively. C p0 of CO2(g), CO(g), and O2(g) at 298
K are 37.11, 29.11, and 29.35 J/mol-K, respectively.
CY11001 Sec13&14 (spring 16) Department of Chemistry
Determine DU0 from DH0
H U   ( pV )
 r H 0  rU 0  p 0  rV 0 (at constant pressure)

The change in volume of a reaction can be obtained from the change in volume of the gaseous
components of the reaction (molar volume of gas > molar volume of solid/liquid)
p0 DrV0 = Drng RT

 r H 0  rU 0  (ng ) RT

CH 4 (g)  2O 2 (g )  CO2 (g)  2H 2O(l )  r H 0  890.36 kJ/mol

P 0  rV 0  r ng RT  2 RT

 rU 0  r H 0  2 RT

RT = 2.5 kJ/mol at 300 K and 8.3 kJ/mol at

For 1000 K! not involving gases, D n = 0. Hence D H0
reactions r g r
= Sec13&14
CY11001 D U0 (spring 16) Department of Chemistry
Determination of DrG0 and DrS0

r H 0  
products
 f H 0  
reactants
 f H 0

r S 0   S m0 
products

reactants
S m0

rG0  
products
 f G 0  
reactants
 f G 0

 r G 0  r H 0  T r S 0

CY11001 Sec13&14 (spring 16) Department of Chemistry

n example snapshot of thermodynamic table

At 298 K

CY11001 Sec13&14 (spring 16) Department of Chemistry

Limitations of the Fundamental Equation of Chemical
Thermodynamics:
dG Vdp  SdT
Does not apply

• When composition is changing due to exchange of matter with surroundings

(open system)
• Irreversible chemical reaction
• Irreversible inter-phase transport of matter
For one phase and multi-component system, in thermal and
mechanical equilibrium but not in material equilibrium, G = f (T, p,
n1, n2, ....),
(T, p, n1, n2, ….)Irreversible (T+dT, p+dp, n1+dn1,
n2+dn2, ….)
 G   G   G   G 
dG   dp    dT    dn1      dni
 p  T, n i  T  p, ni  n1  T, p, n j n1  ni  T, p, n j ni

 G  G is state function, dG is
dG Vdp  SdT     dni same if the process was
i  ni  T, p, n n
j i
reversible
CY11001 Sec13&14 (spring 16) Department of Chemistry
Chemical Potential
 G 
dG Vdp  SdT   i
 
 n 
 i  T, p, n j ni
dni

dG Vdp  SdT    dn
i
i i

Applicable to single phase, multi

i  f T , p, n1 , n2 , ..... component system at thermal and
mechanical equilibrium but not
material equilibrium.
 G  dG p ,T   i dni
i  
 ni  p , T , nJ #i
i

dwadd,max  i dni
i
For pure substance Maximum additional work that can
 (Chemical Potential) = Gm = G/n arise from changing the components
of the system.

CY11001 Sec13&14 (spring 16) Department of Chemistry

 Fundamental Equations of Thermodynamics or Gibbs
Equations - Revisited
n
 U 
dU TdS  pdV   i dni where, i  
i 1  ni  S ,V ,n j
Applicable
n
 H 
dH TdS  Vdp   i dni where, i   to single
 ni
phase
i 1  S , p ,n j multi-
componen
 A 
n
dA  SdT  pdV   i dni where, i   t open
i 1  ni  T ,V ,n j system in
thermal
n
 G  and
dG  SdT  Vdp   i dni where, i   mechanica
i 1  ni  T , p ,n j l
equilibriu
 U   H   A   G  m and pV
i         work only.
 ni  S ,V ,n ji  ni  S , p ,n ji  ni  T ,V ,n j i  ni  T , p ,n j i
CY11001 Sec13&14 (spring 16) Department of Chemistry
Multi-phase Multi-Component System:
For one phase () system,

dG V dp  S dT  
 i

dni 
in thermal and mechanical
i equilibrium pV work only
For multiple
phases
dG  dG  V dp   
 S 
dT     i dni  

    i

 G 
i   
 ni  p , T , nji
Since, S and V are extensive properties,

dG Vdp  SdT    i dni Thermal and

mechanical equilibrium.
 i
p-V work only

CY11001 Sec13&14 (spring 16) Department of Chemistry

 Material Equilibrium

dG Vdp  SdT    i dni Thermal and

 i mechanical equilibrium.
p-V work only
For a liquid and vapor mixture of water and acetone,

dG Vdp  SdT   wv dnwv   acv dnac

v
  wl dnwl   ac
l l
dnac

dG p ,T   i dni Thermal and mechanical

 i equilibrium and constant T and
p. p-V work only
At complete equilibrium (thermal, mechanical,
and material) at constant T and p, pV work only,
dG = 0.
  i i 0

 

i
dn 

CY11001 Sec13&14 (spring 16) Department of Chemistry

hemical Potential and Phase Equilibrium

dG A i , A ( dni ) and dG B i , B dni

dG dG A  dG B (  i , B   i , A ) dni
Change taking
place at constant
T, p
If i , A i , B , then dG  0 • Spontaneous transport of i from
phase A to phase B
If i , A i , B , then dG  0 • Spontaneous transport of i from
phase B to phase A
If i , A i , B , then dG 0 • Phase Equilibrium

• Substance i flows spontaneously from a phase with higher chemical

potential to a phase with lower chemical potential .
Gibbs-Duhem Equation
n 
G p ,T n11  n2  2   
i
i i

dG p ,T    dn   n d
i i i i
i i

dG p ,T   i dni At thermal and

i mechanical
equilibrium.
At constant p and T
 n d
i
i i 0
Gibbs-Duhem Equation

For a binary mixture, n1 dm1 + n2 dm2

Chemical potential of one
= 0
component of a mixture can
not change independently of
Hence, dm1 = - (n2/n1) dm2 the chemical potentials of
other components.
If n >n , a small change in m2 causes
2 1
CY11001 Sec13&14 (spring 16) Department of Chemistry
hemical Potential and Phase Equilibrium
 G 
Chemical potential for a component in a i  
mixture:  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.
CY11001 Sec13&14 (spring 16) Department of Chemistry
ow to construct one-component phase diagrams
ow to construct one-component phase diagrams
ow to construct one-component phase diagrams
A typical phase diagram  Thermodynamic stability

 Metastable states
F?
F?  Phase
F? boundary/Coexistence
curves
F?
 Boiling/melting point
1 atm
F?  Normal boiling/ normal
melting point (1 atm)
F?
 Standard boiling/
standard melting point (1
bar)

 Triple point
Phase Rule: F = C - P + 2
C: # of components
P: # of phases  Critical temperature
F: # of parameters that can be varied
independently
 Phase Diagram of CO2

Melting point of solid CO2 rises with pressure

At normal atmospheric pressure, CO2 can not be liquefied (dry ice).
Department of Chemistry
Phase Diagram of H2O

Department of Chemistry
Phase Diagram of H2O

Department of Chemistry
cation and shape of phase boundaryFor 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)

dp/dT = Sm,trs /Vm, trs dT/dp = Vtrs /StrsThe Clapeyron

dp/dT = Strs /Vtrs Equation
Applies to any phase
Department of Chemistry
equilibrium of any pure
) Solid to Liquid Phase Boundary
dp S trs H fus
 
dT Vtrs Tfus Vfus
f T1 is melting point at p1, and T2 at p2
p2 H fus T2 dT
p1
dp 
Vfus T1 T

H fus T2
p  ln
Vfus T1

T2 T2  T1 T2  T1 T
for, T2 T1, ln ln(1  )  
T1 T1 T1 T1
H fus
p  T
T1Vfus
T1Vfus
T  p
H fus

Melting point (linearly) rises with

pressure
Department of Chemistry
) Liquid to Vapor Phase Boundary
dp S trs H vap
 
dT Vtrs TvapVvap

Vvap = Vm (g) - Vm (l)  Vm (g) = RT/p (for ideal gas)

dp H vap H vap
  (for ideal
dT TVm T ( RT ) / p gas)
dp 1 H vap

p dT RT 2
d ln p H vap Clausius -Clapeyron
 Equation
dT RT 2
ln p 2 H vap T2 dT
 d ln p 
ln p1 R T T1 2

p2 H vap  1 1 
ln  T  
p1 R  2 T1 
H vap  1 1 
p2  p1 exp(   ),   T  
R  2 T1 
Department of Chemistry
 dp S trs H sub
i) Solid to Vapor Phase Boundary  
dT Vtrs Tsub Vsub

Vsub = Vm (g) - Vm (s)  Vm (g) = RT/p (for ideal gas)

d ln p H sub

dT RT 2
p2 H  1 1
ln  sub   
p2 R  T2 T1 
p2  p1 exp(  ),
H  1 1 
  sub   
R T T 
 2 1
H  H
fus vap  1 1 
 
R  T T 
 2 1
Department of Chemistry
cation and shape of phase boundary
One component (pure) system

Clapeyron Equation dT/dp = Vtrs /Strs

T1 Vfus
T  p
Solid to Liquid Phase Boundary 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

 2

dT RT RT 2
Department of Chemistry
mperature Dependence of Chemical Potential:

dG Vdp  SdT
d Vm dP  S m dT

  
   S m
 T  P
S m (solid)  S m (liquid)  S m (gas)

CY11001 Sec13&14 (spring 16) Department of Chemistry

ect of pressure on Melting/Boiling Point
dG Vdp  SdT
  
  Vm d Vm dP  S m dT
 p  T
Vm (solid)  Vm (liquid)  Vm (gas)

Melting point increases Melting point decreases

with pressure when with pressure when
Vm(l)>Vm(s) Vm(l)<Vm(s)

CY11001 Sec13&14 (spring 16) Department of Chemistry

 (isothermal) Pressure dependence of
Chemical
 G  Potential
G p p
G2 G1   Vdp
2

 dG  Vdp
2 2
  V
 p T
G p1
p
1 1

p2
for one component system, 2 (T ) 1 (T ) 
Vp1
m dp

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,
 (T )  (T )  RT ln o
o

p the chemical potential of the

pure gas at 1 bar at temp T.
 (T )  o (T )  RT ln p
p expressed in bar.
Department of Chemistry
hemical Potential of Pure Real Gas
 (T )  o (T )  RT ln f f = fugacity, an
effective pressure in
 o (T )  RT ln p bar=f p
 ideal (T )  RT ln 
f = fugacity coefficient

Z1
p
ln   dp Z = Compressibility
0 p factor
At low pressure,

Z  1  ln   0   real   ideal
 1 f  p
At high pressure,
Z  1  ln   0   real   ideal
 1 f  p
Department of Chemistry
e Gibbs Energy of Mixing of Ideal Gases
i (T ) i o (T )  RT ln pi pi = partial pressure of ith gas in
bar.
Before mixing:
Gbefore mixing   
i
ni io (T )  RT ln p 
After mixing:
Gmixture   
 i
ni i 
i
ni i o (T )  RT ln pi 
 n  (T )  RT ln  p 
i i
o
i
i
Dalton’s law of
partial pressure,
p i= c ip
Gmix nRT  i
i ln  i Gibbs free energy of mixing
of ideal gases is always
negative, and hence
spontaneous
Department of Chemistry
e Enthalpy of Mixing of Ideal Gases

Gmix nRT  i ln  i
i

 Gmix 
S mix     nR  i ln  i
 T  p ,n i

H mix Gmix  TS mix 0

Ideal gases show no

intermolecular interactions
and hence change in
enthalpy is zero
Department of Chemistry
emical Potential of Liquids: Ideal Solutions

* means pure
*

 A,l  A, g  A0 , g  RT ln p A
 *A,l  *A, g  A0 , g  RT ln p *A
 A,l  *A,l  RT ln p *A  RT ln p A
 A0 , g  *A,l  RT ln p *A
pA
 A , l  *
A ,l  RT ln *
pA
pA
 A , l  *
A ,l  RT ln *
p*A vapour pressure of pure A(l)
pA
pA vapour pressure of A(l) in a
Relationship between ratio mixture
of vapor pressures and
  G 
dG Vdp  SdT  i
 
 n 
 i  T, p, n j ni
dni

dG Vdp  SdT    dn
i
i i

dG p ,T    dn
i
i i

 (T )  o (T )  RT ln p
 (T )  ideal (T )  RT ln 

pA
 A,l  *A,l  RT ln
p*A
Raoult’s Law
pA The ratio of partial vapor
 A
p*A pressure of each component to
its vapor pressure as a pure
p A  A p*A liquid is equal to the mole
fraction A in the liquid mixture
(cA).
Ideal solutions obey Raoult’s law for the
entire range of mole fraction, from pure A to
pure B
 A,l  *A,l  RT ln  A For ideal solution -
 B ,l  B* ,l  RT ln  B solvent & solute both
obey Raoult’s law

*
pA  p*A  A,l   A,l
The vapor pressure (and chemical potential) of the solvent in the solution is
lower than that of the pure solvent
Ideal-Dilute Solutions
Henry’s Law: In dilute solution,
pB   B but p B   B p B*
for solute , B
p B  B K B
For practical applications KB = Empirical constant (dimension of
p B bB K B bB = molality of B p) called Henry’s law constant

Solutions in which solvent obeys Raoult’s law

and solute obeys Henry’s law is an Ideal-
Dilute solution
 B  B*  RT ln( pB / p*B )
*
 B  RT ln(  B K B / p*B )
*
 B  RT ln( K B / p*B )  RT ln  B
 B0  RT ln  B
if p*B K B   B0  B*
l Solutions: (Activity, the effective mole fraction)
The Solvent The Solute
Activity* Activity:
p
 A  A  RT ln *A  B  B*  RT ln
pB
pA p*B
For ideal solution (Raoult’s law) For Ideal Dilute Solution (Henry's law)
 A  *A  RT ln  A  B  B0  RT ln  B

For real solution For real solutions,

 A  *A  RT ln a A
pA  B  B0  RT ln aB
aA 
p*A
a A  A as  A  1
aB B  B
aB   B and B  1 as  B  0
a A  A  A ;  A  1 as  A  1

gA is activity coefficient
Summary
Ideal Solution i (T ) i* (T )  RT ln  i
* means pure

Ideal-Dilute Solutions

 A (T )  *A (T )  RT ln  A
A= Solvent,
B= Solute  B (T )  B0 (T )  RT ln  B 0
means
Standard state
 B (T )  B0 (T )  RT ln bB
Real Solutions

For solute  B  B0  RT ln aB aB B bB ; B  1 as bB  0

For solvent
 A  *A  RT ln a A a A  A x A ;  A  1 as x A  1
ect of solute on boiling and melting points of solve

*
 A  A  RT ln  A

 A  *A  RT ln a A
hermodynamics of Simple Mixtures

Partial Molar Volume

1 mol of water added to a huge volume of water increases the volume by 18
cm3. Vm=18 cm3/mol
1 mol of water added to a huge volume of ethanol increases the volume
by 14 cm3. Vm=14 cm3/mol
 V 
Vi  
 Partial Molar Volume Can be +ve, -ve, or 0!
 ni  p , T , n j i

 V   V 
dV  
 dn A   
 dnB V Adn A  VB dnB
 ni  p, T , nB  ni  p, T , n A

nA nB


V  V Adn A 
0
V dn
0
B B V An A  VB nB

G p ,T n11  n2  2    n 
i
i i

CY11001 Sec13&14 (spring 16) Department of Chemistry

Gibbs-Duhem Equation
n 
G p ,T n11  n2  2   
i
i i

dG p ,T    dn   n d
i i i i
i i

dG p ,T   i dni At thermal and

i mechanical
equilibrium.
At constant p and T
 n d
i
i i 0
Gibbs-Duhem Equation

For a binary mixture, n1 dm1 + n2 dm2

Chemical potential of one
= 0
component of a mixture can
not change independently of
Hence, dm1 = - (n2/n1) dm2 the chemical potentials of
other components.
If n >n , a small change in m2 causes
2 1
CY11001 Sec13&14 (spring 16) Department of Chemistry
Mixing of Ideal
Solutions
Gi n A  *A  nB  B
*
  
Gf n A  *A  RT ln  A  nB  B
*
 RT ln  B 
Ideal solution – Raoult’s
Gmix nRT   ln 
i
i i law
Leading to ideal solution, similar to
S mix  nR   ln  i i mixing of ideal gases.
i
H mix 0 InteractionAB = InteractionAA
 Gmix  =InteractionBB
Vmix   0
 p T Excess enthalpy
(benzene+cyclohex
Mixing of Real ane)
Solutions (excess
functions)
S E S mix  S mix (ideal )

Excess entropy
InteractionAB < InteractionAA
InteractionAB < InteractionBB
Reaction Gibbs Energy (DrG)
A B
t 0 1 0
t t 1  d d
dn  d  d dx is the extent of reaction.

dG  Adn A   B dnB   Ad   B d (  B   A )d

 G 
   B   A
   p ,T

The reaction Gibbs energy is

 G  the difference between the
 r G    B   A chemical potential of product
   p ,T and reactant at the
composition of the reaction
mixture.
Reaction Gibbs Energy (DrG)
aA  bB  cC  dD
exergonic
 G 
 r G   cC  d D   a A  b B 
   p ,T endergonic

 G 
 r G  
   p ,T
  
i
i i

CH 4 (g)  2O 2 (g )  CO 2 (g)  2H 2O(l )

  
 r G  2  H 2O (l )  CO2 ( g )  CH 4 ( g )  2 O2 ( g ) 
At equilibrium,

 i
i i 0 Condition for chemical reaction equilibrium.
At the reaction equilibrium, the chemical potentials
of the product balance those of the reactants
Reaction Equilibrium 
rG   i
 i i  i
 i [ i0 (T )  RT ln ai ]

  0
i i (T )   RT ln ai i
i i

 r G (T )  r G 0 (T )  RT ln  i
ai i  r G 0 (T )  RT ln Q

Q i
ai i The reaction Quotient
(at any extent of the reaction)

At equilibrium,
 
Thermodynamic
K   i 
ai
equilibrium constant

 i

 at equilibrium  r G 0  RT ln K
 r G (T ) 0  r G 0 (T )  RT ln K Can be used to calculate
equilibrium constant for
any reaction from tables
Practically ai approximated by numerical values of
of thermodynamic data.
molalities / by molar concentration / numerical values of
action Equilibrium in ideal gas reaction
aA( g )  bB( g )  cC ( g )  dD( g )
 r G (T )  r G 0 (T )  RT ln Q

i The reaction Quotient

 pi 
Q a  i
i
 
 p0 
 
in terms of partial
i i pressure
(at any extent of
At equilibrium, reaction)
 p0 = 1 bar
 pi  i
Kp   i
  (at equilibrium)
 p0 
 

 r G (T ) 0  r G 0 (T )  RT ln K p

 r G 0  RT ln K p
Different types of equilibrium constants
  Thermodynamic equilibrium constant in
K 
 a i 
i

terms of activity coefficients (ai)
 i  equilibrium

  Standard equilibrium constant for gaseous

Kp 
  pi i 

reaction
pi (in bar units)
 i  equilibrium

 
K c 
  ci i 

Standard concentration equilibrium constant.
ci in mol/L
 i  equilibrium

 
K  
  i i 

Mole-fraction equilibrium constant
 i  equilibrium
Response of equilibria to pressure change
A( g )  2 B ( g )
t 0 1 0
at eqlbr 1  2 a is the degree of
dissociation
1  2
i
1 1
1  2
pi p p p is in bar
1 1
i
 pi  4 2
Kp   i
 
 p0 
 

1 2
p

 K p 
But we know,   0

1/ 2
 p T
 
 
 1 
  
4p
 1  Le-Chatelier principle
 Kp 
 
Temperature dependence of equilibrium
constant
0
 r G  RT ln K

d ln K

0
1 d rG / T 
dT R dT


d rG0 / T    H
r
0
(Gibbs Helmholtz Equation)
dT 2
T
0
d ln K  r H van’t Hoff equation

dT RT 2

For exothermic reactions, K decreases with increasing T

r H 0  1 1
ln K 2  ln K1    
R  T2 T1 

Thermodynamics can tell us if a process is possible, but
signifies nothing about how fast the process will occur.

Thermodynamics treats only the equilibrium properties of the

system; Kinetics determines the pathway by which
equilibrium is reached.

Transport (in space) processes constitute Physical Kinetics,

e.g., thermal conduction, fluid dynamics, diffusion, electrical
conductivity

A chemically reacting system is not in equilibrium. Study of

rates and mechanisms of chemical reactions constitutes
Chemical Kinetics.

Applications of Chemical Kinetics in environmental

protection, chemical/pharmaceutical industries, automobile
industries, etc.
The Rates of Reactions
A + 2B 3C + D
1 d[I ] The instantaneous rate of consumption/formation
R
 i dt is the rate of reaction

d [ A] 1 d [ B ] 1 d [C ] d [ D ]
R    
dt 2 dt 3 dt dt

For, N2 + 3 H2  2NH3

R= -d[N2]/dt = -1/3 d[H2]/dt = ½ d[NH3]/dt

Units of R, molar concentration per time

 The Rate Laws A + 2B 3C + D
overall reaction order = a + b
R   A B 
 
Partial orders a, b
k = Proportionality constant =
R k  A B 
 
rate constant (independent of
concentrations)
Rate Law in terms of concentrations.
R  f ([ A], [ B ], .....) Empirically determined from reaction rates.
Can not be obtained from stoichiometry
Examples:
Determination of the rate laws
A + B  Products
Isolation method: Concentrations of all but one reactant are in large
excess

R k  AB k  AB 0 k ' A Pseudofirst-order rate law

Method of initial rate:

R k  A B  k  A B 0 k '  A
    

R0 k '  A0


log R0 log k ' log A0

log R0

B is present in large excess,

and initial concentration of A is
[A]0. R0 is initial rate.
log A0
Integrated rate laws

1st order aA b B

1 d [ A]
R  k[ A]
a dt
d [ A]
 k A [ A]
dt
[ A ] d [ A] t
  k A dt
[ A ]0 [ A] 0

[ A] [ A]0 exp( k At )
Integrated rate law
for 1st order reaction
t1/ 2 0.693 / k A
Half life period is independent of
concentration for a first order
reaction
Chemical Kinetics
naA + nbB ncC + ndD
1 d[I ] The instantaneous rate of consumption/formation
R
 i dt is the rate of reaction

overall reaction order = a + b

R   A B 
 
Partial orders a, b

R k  A B 
  k = Proportionality constant =
rate constant (independent of
concentrations)

Integrated Rate Law for 1st order reaction

aA b B

[ A] [ A]0 exp( k At )
t1/ 2 0.693 / k A
Integrated rate laws

2nd order aA b B

Concentration of A
approaches zero
1 d [ A] more slowly in 2nd
R  k [ A]2
a dt order reaction than
in a 1st order
d [ A]
 2
k A dt reaction.
[ A]
[ A] d [ A] t
[ A ]0

[ A] 2
k A dt
0

[ A]0
[ A] 
1  k At[ A]0
For aA +bB  pdt

1
1 d [ A]
t1/ 2   k[ A][ B ]
k A [ A]0 a dt
[ B ] /[ B ]0
ln a[ B ]0  b[ A]0  kt
[ A] /[ A]0
Integrated rate laws

For nth order reaction,

n1 1  1 1 
kA    
d [ A] n 1
t (n  1)  [ A]t [ A]0n  1 
 n
k A dt
[ A] 2n 1  1
t1/ 2 
(n  1)k A [ A]0n  1
 Reversible First Order Reactions NH 4 SCN CS(NH 2 ) 2
k1
A B d [ A] d [ B]
k2  k1[ A]  k 2 [ B ] k1[ A]  k 2 [ B ]
dt dt
at t=0, [B]= 0 and [A] =
[A]0
[ A]  [ B ] [ A]0 at t=t, [B]= [A]0 - [A]

d [ A]
 k1[ A] k 2 [ A]0  k 2 [ A] k 2 [ A]0  (k1  k 2 )[ A]
dt

k 2  k1 exp( (k1  k 2 )t )
[ A]  [ A]0
k1  k 2
Reversible First Order Reactions
k1
A B
k2
k 2  k1 exp( (k1  k 2 )t )
[ A]  [ A]0
k1  k 2

at t = 
k2
[ A] [ A]eq  [ A]0
k1  k 2

k1
[ B ] [ B ]eq [ A]0  [ A]eq  [ A]0
k1  k 2

[ B ]eq k1
K 
[ A]eq k 2 Equilibrium Constant in
terms of rate constants
k1[ A]eq k 2 [ B ]eq
 Consecutive First Order Reactions
k1 k2
A  I  P
at t=0, [A]= [A]0 , [I]=0 , [P]=0

At any time t
[ A]  [ I ]  [ P ] [ A]0
The rate of decomposition of A
d [ A] [ A] [ A]0 e  k1t k1=10*k2
 k1[ A]
dt
The rate of formation of I
(from A and decomposition to P)
d[I ]
k1[ A]  k 2 [ I ] [I ] 
k 2  k1

k1[ A]0  k1t
e  e  k 2t 
dt
he rate of formation of P (from I)
d [ P]  k1e  k 2t  k 2 e  k1t 
k 2 [ I ] [ P ] [ A]0 1  
dt  k 2  k 1 
 The Steady State Approximation k1 k2
A  I  P
Useful for multi-step reactions where the rate laws become too complex
• During the major part of the reaction (except for the initial induction
period), the rates of change of concentrations of all intermediates
are negligibly small

d[I ]
0 for all intermediates
dt
d[I ]
k1[ A]  k 2 [ I ] 0
dt k2=20*k1
k1
[ I ]  [ A]0 exp( k1t )
k2
d [ P]
k 2 [ I ] k1[ A]0 exp( k1t )
dt
[ P ] [ A]0 1  exp( k1t ) 
Rate Determining Step
k1 k2
A  I  P
 k1e  k 2t  k 2 e  k1t 
[ P ] [ A]0 1  
 k 2  k 1 


k 2  k1  [ P ] [ A]0 1  e   k1t

k1  k 2  [ P ] [ A] 1  e  0
 k 2t

The slowest step is the rate

determining step