CY 11001 CHEMISTRY

Teacher: Prof.
P.K.Chattaraj
Office: Room C-301D(2nd Floor,ChemistryDepartment)
e-mail: pkc@chem.iitkgp.ernet.in
phone: 83304 (office)

Ground Rules for the Class

• Mobile Phones in switched off mode
• Attendance is a must and will be checked regularly
• Vast syllabus and fast paced, advised to take class notes
 CLASS SCHEDULE

Chemistry theory (CY11001) for Sections 1 & 2:

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Physical: 31.07.2017 (Mon) to 24.08.2017 (Thurs) - 15 hours

Inorganic: 29.08.2017 (Mon) to 12.10.2017 (Thurs) - 15 hours

Organic: 16.10.2017 (Mon) to 16.11.2017 (Thurs) - 14 hours

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CLASS TIMINGS:
Monday 12:00 – 12:55 pm
Tuesday 10:00 – 11:55 am

EXTRA CLASS: 31.07.2017 to 25.08.2017 (Thursday 2:00 – 2:55 pm)

 Tutorial class: Tuesday 4 – 4:55pm

Section 1A: 10AG10032 to 17EE10038 NC 121

TA: Dr. Siddhartha Pal

Section 1B: 17EE10054 to 17QD30009 NC 122

TA: Dr. Dipankar Mondal

Section 2A: 16GG20007 to 17CH30010 NC 233

TA: Sultana Parveen

Section 2B: 17CH30026 to 17GG20022 NC 234

TA: Gargi Biswas
Distribution of Marks:
Mid Semester (Only Physical): 30%
End Semester (Inorganic & Organic): 50%

Teachers Assessment (TA):

20% [Physical (6%), Inorganic (7%), Organic (7%)]

TA marks to be based on a continuous evaluation system - MOODLE

Text Book:
Atkin’s Physical Chemistry 8th/9th Ed
Reference Books:
Physical Chemistry: Silbey Alberty Bawendi - John Wiley &
Sons, Inc.
Physical Chemistry: Levine, McGraw-Hill Book Company
Physical Chemistry David W Ball; Thompson.
 CY 11001 CHEMISTRY (L-T- P: 3-1-0; Credit : 4)
Thermodynamics of Chemical Processes:
• Review of Essential Concepts and Definitions
•Revision: Heat, Work & Energy; First Law of Thermodynamics
•The Second Law of Thermodynamics
•Concept of Entropy
•Gibbs Free Energy
•Equilibrium conditions for Closed Systems
•Maxwell Relations
•The Chemical Potential
•Definition and Concept of Open Systems
•Phase and Reaction Equilibria
Electrochemical Systems:
•Electrochemical Cells and EMF
•Applications of EMF Measurements: Thermodynamic data, Activity
Coefficients, Solubility product and pH
Chemical Kinetics:
•Reversible, Consecutive and Parallel reactions
•Steady state approximations; Chain reactions
 Thermodynamics

Thermodynamics provides a framework of relating the macroscopic properties

of a system to one another.
Thermodynamics: ↔ Classical, Statistical and Irreversible
Classical Thermodynamics is the study of macroscopic properties
of system/matter at equilibrium (which does not change with time) using the
laws governing transformation of energy from one form to another.
It is concerned only with macroscopic quantities and
ignores the microscopic variables that characterize individual
molecules.

THE BASIC CONCEPTS:

System: Part of the Universe, the properties of which is of interest.
Surroundings: the region outside the system where we make our
measurements.
Boundary, a hypothetical/real barrier between system and surroundings.
 Thermodynamic Systems

Open systems can exchange both matter and

energy with the environment.
Closed systems exchange
energy but not matter with
the environment.
Isolatedsystems can exchange neither energy
nor matter with the environment.
 Thermodynamic Systems

 System : Open, Closed, Isolated

 Surroundings
 Boundary / Wall
• Rigid and Non rigid (movable)
• Permeable and Impermeable (no matter is allowed to pass through it)
• Adiabatic and Diathermic boundary (- permits the passage of energy
as heat )

A system surrounded by a rigid, impermeable, adiabatic wall –

ISOLATED SYSTEM ;

Example: Universe as a whole, a thermo flask

 Thermodynamic Equilibrium

Equilibrium thermodynamics deals with systems in Equilibrium Isolated

System is in Equilibrium when its :

a) Macroscopic properties do not change with time

Non Isolated system is in Equilibrium when its:

a)Macroscopic properties do not change with time
b)Removal of the system from contact with its surroundings can causes no
change in the properties of the system
•A system in thermodynamic equilibrium is an Equilibrium System
•Thermodynamic State only defined by the present values of the state
variables, not by the history.

What are conditions of Thermodynamic Equilibrium?

 Mechanical Equilibrium

The condition of equality of pressure on either side of

a movable wall / boundary.

No unbalanced forces act on or within the system –

does not undergo acceleration or, no turbulence inside
the system
Mechanical equilibrium between system and the
surroundings, is a condition in which there is no
change in the properties of the system or
surroundings when they are separated by a movable
wall / boundary.

Here, we are ignoring the effect of the earth’s gravitational field, which causes a slight increase in
pressure as one goes from the top to the bottom of the system.
 Thermal Equilibrium

Thermal equilibrium between system and

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

In other words, Thermal Equilibrium

is a condition in which no change of state
occurs when two objects A to B are in
contact through a diathermic boundary.

Systems in mechanical equilibrium with

each other have the same pressure. What
about systems that are in thermal
equilibrium with each other?
 A very important macroscopic parameter: Temperature

Temperature is a property associated with random motion of many

particles. Introduction of the concept of temperature in thermodynamics is
based on the the 0’th law of thermodynamics:

B acts as Thermometer.
A, B, C all are at the same “temperature”.

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.
 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
Phase: a homogeneous part of a system is called a phase

For thermodynamic equilibrium, all the three kinds of equilibrium must be

present
No matter what is the initial state of an isolated system, eventually it
will reach the state of thermodynamic equilibrium
 How to define a Thermodynamic State of a System?
What properties does thermodynamics use to characterize a system in
equilibrium?

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 phases,
•pressure (P), volume (V), Temperature (T), density, etc.
•field strength, if magnetic/electrical field act on the system
•gravitational field
(N.B.: only the average values are considered, all fluctuation and perturbations
are ignored).
On the other hand, Microscopic state of a system needs description of each
molecule – a very complicated picture
 Thermodynamic Systems

Intensive properties
Does not depend upon size (the quantity/amount of matter present) of
the system [e.g. Pressure, Temp, Viscosity, Density etc.]
Total Property = property of part of the system
Extensive properties
Depends upon size of the system [e.g. n, V, surface area etc ]
Extensive properties depend on the amount of substance in the system.]
Total Property = Σ property (in each part of the system)
Other variables:
Compositions, Surface area, Electrical/magnetic strength Gravitational
field can/are generally ignored

Homogeneous system, a system having its intensive

macroscopic
properties uniform throughout – a single phase solution / pure.
Heterogeneous system, a system with more than one phase.
Thermodynamic State Variables / Properties
 Thermodynamic State Variables / Properties

Therefore, for describing the State of a System we require:

• A few experimentally measureable macroscopic properties: p, T, V, n, m, ...
• Knowledge if System is Homogeneous or Heterogeneous
• Knowledge if System is in Equilibrium State
• Knowledge of the number of components
 Thermodynamic State
If the value of every thermodynamic property in system A is same as in system B –
then they are in the same thermodynamic state

The state of a thermodynamic system is defined by specifying the values of

its thermodynamic properties – However, it is not necessary to specify all the properties
to define the state of a system.

In fact, the macroscopic state of a system can be specified by the values of a small
number of macroscopic variables – these called the Properties / Parameters /
Thermodynamic variables of a system.

For instance: The thermodynamic state of a single-phase system of fixed amounts of

non reacting substances can be described by any two of the three state functions
(P, V and T)

Equation of state, an equation that interrelates

pressure, volume, temperature, and amount of substance: P = f (T, V, n).
 The Equation of State of Ideal Gases
An equation of state - an equation that relates macroscopic variables
(e.g., P, V, and T) of a given substance in thermodynamic equilibrium.

In equilibrium ( No macroscopic motion), just a few macroscopic

parameters are required to describe the state of a system.

Geometrical representation of the equation of state: f (P,V,T) = 0

an equilibrium
P state
The ideal gas equation of state: PV  nRT

P – pressure [Newtons/m2]
V – volume [m3] the equation- of-
n – number of moles of gas state surface

T – the temperature in Kelvins [K]

J
R – a universal constant R  8.31
mol  K V

T
 Thermodynamic Process: Operation for Change in State

Change of State: Transformation

e.g., 3 H2 (g, 5 bar, 100 °C) → 3 H2 (g, 1 bar, 50 °C)
(initial state) (final state)
Path: Sequence of Intermediate states, arranged in order, through which
a system passes to attain the final state

Process: Operation through which a system undergoes a change in state.

Process describes the path.
Path
Path can be:
 Reversible (always in Equilibrium)
 Irreversible (describes direction of time)
 Cyclic(initial and final state have the same value)
Processes can be:
• Adiabatic (No heat transfer between system and surrounding)
• Isobaric (Constant pressure process)
• Isothermal (Constant temp process)
• Constant Volume process • Endothermic & Exothermic process (q<0 & q>0)
 Essential concepts / Definitions
Processes : When one or more of the parameters of a system changes, the state of the
system also changes and the system is said to have undergone a process.

Various types of processes:

•Isothermal (T),
•Isobaric (P),
•Isochoric (V)
•Adiabatic (q),
•Isenthalpic (H)
•Exothermic & Endothermic
•Cyclic

Each process can be

either carried out
Reversibly or
Irreversibly
 Thermodynamic Processes can be: :

Spontaneous Processes (Irreversible

Process)
•Spontaneous processes are those that can
proceed without any outside intervention.

•The gas in vessel B will spontaneously effuse

into vessel A, but once the gas is in both vessels,
it can not spontaneously go back to B

• Irreversible processes cannot be undone by exactly reversing the change to

the system.
• All Spontaneous processes are irreversible.
• All Real processes are irreversible.
Thermodynamic Processes can be :

Reversible Processes
In a reversible process the system changes
in such a way that the system and
surroundings can be put back in their
original states by exactly reversing the
process.

Changes are infinitesimally small in a

reversible process.

Quasi thermodynamic equilibrium, at

each of the small stages
 Partial Differentiation: A primer

Consider a function of two variables f

(x,y)

Definition: A partial derivative of one of the

variables: the rate of change of the
function
w.r.t. that variable with all other variables
kept fixed.
df
  f = f (x,y), f ( x  x, y )  f ( x, y )
Suppose:
 dx   Limx 0
 y x

 df  f ( x, y  y )  f ( x, y )
 dy   Limy 0
 x y

 f   f 
 For example: f (x, y) = x2y
 x   2xy,  y   x 2

y  x
 Properties of partial derivatives

Consider a function of two variables  f (x, y)

 Its differential form will be:

 df   df 
df    dx    dy
 dx  y  dy  x

•Two partial derivatives operating on a function:

Let f be function of two variables, i.e., f = f (x, y);
Double partial derivative of the function f can be written as:
  df   2f  2f  2f The exact differential
   
x  dy  x x y x y y x

2
Verification: Let the function be: f ( x , y )  x y ,
 2f  2f The exact differential
 2x,  2x,
y x y x
 Properties of partial derivatives

•The Chain rule:

Let s be an independent parameter and if change of s results

in changes in the values of x and y.

i.e., x = x (s); y = y (s);  we can write, f (x, y)  f (s)

df   df  dx   df  dy
   
ds  dx  y ds  dy  x ds

•In general, the total differential form of f(x,y) may be written as:
df  M( x , y )dx  N ( x , y )dy
 f 
M   f  and
where ,
N   
 x  y  y x
 Properties of partial derivatives

 Does any differential form of type [M(x,y)dx + N(x,y)dy] always

represent the total differential form of a function?

Only if   M 
  N 
 y   x 
 x  y

If above is true then, df = [M(x,y)dx + N(x,y)dy] represents an

exact differential.

Example:
Let us consider: 3 x y dx  2 x ydy
2 2 3
where,
M( x , y )  3 x 2 y 2
, N( x, y )  2x3y
It can be easily verified that the above expression corresponds to an
exact differential function of the type:

3 x 2 y 2dx  2 x 3 ydy  d ( x 3 y 2 )
 Properties of partial derivatives
• The Cyclic Rule:

If z is a function two variable, then we can write: z = z (x, y),

 dy   dz   dx 
then,        1
 dz  x  dx  y  dy  z

Example:
If V = f (p, T); p = f (V, T); T= f (p, V), then we can write
 dp   dT   dV 
 dT   dV   dp   1
 V  p  T

Example 1:  dp   nR ;  dT   p ;  dV  nRT
 dT     
Use the Equation of state for  V V  dV  p nR  dp T p2
Ideal gas to verify the cyclic  dV   nR   p  nRT 
rule   dp   dT   dp    V nR
 dT V  dV  p  T     p2 
p = nRT/V; V= nRT/p; T=
pV/nR  nRT 

  pV   1
 
 Properties of partial derivatives

Consequence:
Let us move from a point (xi,yi) to another point
(xf,yf) The corresponding change in f(x,y) can be
written as:

 The VALUE OF THE INTEGRAL OF AN EXACT DIFFERENTIAL is

INDEPENDENT OF THE PATH taken in going from initial to final point
and DEPENDS only on the values of f(x, y) at the initial and the final
points.

NOTE:
Integral of an exact differential function,df, for a closed path (i.e., cyclic)
where, i (initial state) = f (final state):  df  0
 Test for Exactness (State Variable)

If z  f( x, y), dz will be a perfect differential

when it is found 
  z  dx z 
then , dz       dy
  x y   y x  dz is a single-valued function
depending entirely on the
 z   z  instantaneous values of x and
if,    M ; and    N
 y x
y.
 x y  dz between any two specified points or
then, dz  M( x, y )dx  N( x, y)dy states is independent of the path
of transition.

 dzfor a complete cyclic process is

Then for exact differential,
equal to zero
 M  N 
      δq and δw are NOT EXACT
  y x   x y differential quantities therefore
   z     z   they are NOT STATE Va
i.e.,          riables. They are PATH
 y   x y x  x   y x y FUNCTIONS.
 Properties of partial derivatives

1. The Integral of the differential of a state function along any

arbitrary path is simply the difference between the values of
the function at two LIMITS; i.e., b dU  U U
b a
a
Since the integral is path-independent, the differential of a state function is called an Exact
differential

2. If the integrals of any differential of a function depends on the path chosen to go from
the initial to the final state, the differentials are called Inexact differentials i.e.,
b

 w  w
a

3. The sum of two inexact differentials can be an Exact differential . Illustration:

The path is defined by a curve y = y (x) between points 1 and 2

Case 1: let dz = y dx and it is NOT an exact differential then

2 2

  z  z   y dx  Area I
1 1
 Properties of partial derivatives

Case 2: let dz = x dy and it is NOT an exact differential then

2 2

1 z  z  1x dy  Area II

2 2 2 2

 z  z   xdy  Area II

  z  z   ydx  Area I
1 1
1 1

Case 3: dz = y dx +x dy = d (xy)
 dz is an exact differential and
2 2

1 d z   z  1 d (xy)  x2 y2  x1 y1
2 2 2
Also,  d z   y dx   x dy  Area I  Area II
1 1 1

Therefore, the sum of these areas is independent of the path between 1 and 2
therefore, SUM of two path function results in a STATE function
 Energy, Work and Heat
Energy is the capacity to do work.
Energy classification into:  kinetic potential (by
(by motion) position)
Is purely arbitrary! e.g.therma chemical, electrical
l
•Heat and work are “types” of ENERGY, but are processes involving
NOT TRANSFER of
energy
• They appear and disappear at the system boundary. They are path
variables.
• Heat is the transfer of energy from one body to another based on
temperature difference. They are path variables.
• Heat stimulates random motion.
• Convention: if heat flows into the system, q > 0.

• Work is the transfer of energy by some mechanism other than temperature

difference.
• They appear and disappear at the system boundary. They are path
variables.
• Convention: if work is done on the system, w > 0.
• Work stimulates organized motion.
• Work “degrades” into heat.

 Qualitative observations by Count Rumford (Ben Thompson)

 Energy
Concept of Internal Energy
• E= K+ V + U
where, K and V are the macroscopic (not molecular)
kinetic and potential energies of the system

•U is the internal energy of the body (due to molecular motions and

intermolecular interactions)

• Internal Energy,U, is the total kinetic energy due to motion of

molecules (translational, rotational, vibrational) the total potential
energy associated with the vibrational and electric energy of
atoms within molecules or crystals.

•U (molar internal energy) = U/n, where n = no. of moles of the

m
substance

• Um =
Urest, m
Utr, m + Urot, m + Uvib, m + Uinternal, m +

(where, Urest, m = rest mass energy of electrons & nuclei = mrelC2=

 Energy
Properties of Internal Energy

•U is a State function, a property that:

Depends only on the current state of the
system and is independent of how or through path
that state has been reached.

•It is an exact differential and its fundamental

variables are V and  T
U 
dU  dV   U 
U = f (V, T);  V   dT
 T   T V

• For cyclic process,   dU  0

• U is an Extensive property
 The First Law of Thermodynamics
Law of conservation of
energy
A system can contain
only internal energy.
– A system does not contain
heat or work.
– These only occur during a
change in the system. The
sum of the heat, q,
transferred to a system and
the work, w, performed on
it equals to the total change
 Equivalently, perpetual motion machines ofin the thesystem’s kind are
first internal
impossible. A hypothetical machine that can energy,
do/dUproduce work
indefinitely without an energy source / without the input of energy. It
 When energythe
thus violates passes, as work,
first law as heat, or with the
of thermodynamics: matter,
law into or out fromof
of conservation a system,
the system's internal energy changes in accord with the law of conservation of
energy.
energy. process  dw = dU
Adiabatic Cyclic process
 dU  0
 1st Law of Thermodynamics

Consider an example system of a piston and

cylinder with an enclosed dilute gas
characterized by P,V,T & n.

What happens to the gas if the piston is

moved inwards? Compression

•If the container is insulated the temperature

will rise, the atoms move faster and the
pressure rises.

•Is there more internal energy in the gas?

Yes ∆x
External agent did work in pushing the piston
inward.
w = - F  d = -(PA)  (-Δx)
w = P Δ V
Work done on the gas equals the change in
the internal energy of the gas w = Δ U
 1st Law of Thermodynamics

• Change the situation:

• Keep the piston fixed at its original location.
• Place the cylinder on a hot plate.

What happens to gas?

• Heat flows into the gas.
• Atoms move faster, internal energy
increases.
• Q = heat (in Joules) flows in
ΔU = change in internal energy in Joules.
Q = ΔU
 1st Law of Thermodynamics

F
What if we added heat and pushed the piston in at the same
time?

•Work is done on the gas,

•Heat is added to the gas and
•the internal energy of the gas increases:
ΔU = w + Q

U INCREASES with INCREASE in TEMP. of the system, when:

1. work is done on the system by the surrounding or,
2. heat flows into the system from the surrounding or,
3. both, heat and work flows from the surr. into the system
 1st Law of Thermodynamics: Sign convention
 Work done onthe system by surr + ve i.e., Compression
 Work done by the system on surr - ve i.e., Expansion

Alternate Statement: If a system is subjected to a CYCLIC

transformation the work produced in the surroundings is EQUAL to the heat
withdrawn from the surroundings.

Q = - w (change in U is zero as it’s a State function)

If w is +ve (compression, work done on the system) then q will be –ve (heat
will be released by the system) and vice versa
 The First Law of Thermodynamics: Work, Heat & Energy

T1 → T2

T1 → T2
h

Joule Heat Equivalent

Joule Equivalent of Heat: 1 cal = 4.184 J
Experiment
 State and Path Functions

 Some state functions, e.g., U and H etc.

– Value of a state function is independent of path Path 2 -
Non-
– Depends only on initial and final state, adiabatic
Path 1 - w≠0;q≠0
e.g.ΔU = Ufinal – Uinitial Adiabatic
w≠0;q=0
–Overall Change
final

U  initial dU  dU is an exact differential

 Path from initial to final state has a functional

dependence
– For ΔU, work may be done, or, heat may flow or, both
ΔUpath1 = ΔUpath2 = Uf -Ui
– Equations that describe how you get to final state are path
functions
–Path functions
final are path specific
q  initial,path q  q is an inexact differential
 Is Work a STATE FUNCTION?

Assume a Reversible process so that pext = p where, Ar (gas) under goes

change of state through compression, from
Ar (g, p1, V1) (initial) → Ar (g, P2, V2) (final); such that V1> V2 and p1< p2

 V2 )

Compression through two paths 1st Path:

Ar(g, p1, V1) → Ar(g, p1, V2) → Ar(g, p2,
First V1 → V2 when p held constant at p1;

]
then p1 → p2 when V held constant at V2

2nd Path:
Ar(g, p1, V1) → Ar(g, p2, V1) → Ar(g, p2, V2) First p1 → p2
when V held constant at V1;
then V1 → V2 when p held constant at p2

Note for the closed cycle, total work = w[path (1)] - [path
(2)
 Is Work a STATE FUNCTION?

NOTE:
Work done on the system to compress it is NOT EQUAL
through the two paths. i.e., w(1) ≠ w (2)
 Net work done on the system in the complete cycle ≠ 0
i.e., [w(1) - w(2)] ≠ 0;
 w 0 (closed cycle)
 This means w is NOT a state function  we CAN NOT write
w = f(V, p)
 Work
• Expansion work, work of expansion (or compression)
• Non-expansion / additional work: any other work

where

 pex = external pressure

 A = piston area
 dz = displacement
 dV = Adz = volume change for the gas

Total work done,

+ ve
 Work done on the system  i.e., Compression

 Work done by the system  - ve i.e., Expansion

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

F= mg
pex= mg/A
piston held down by pins

F= pex.A

m dz

Area =A

Pi , V i Pf , Vf

w = - mg.A.dz
w = - mg.dV
w = - pex.dV =-pex (Vf-Vi)
0 ≤ Pext ≤ P2

Irreversible
Expansion

P1 ≤ Pext = P2

Irreversible
Compression
Thus, more work has been produces in MULTI stage expansion than in the single stage expansion

Thus, less work is destroyed in MULTI stage compression than in the single stage compression
Maximum and Minimum quantity of Work:

For Work to be maximum, Pext should be largest possible at each stage of the process If the gas is to
EXPAND Pext must be less than pressure of the gas, say P .

Therefore, to obtain maximum work, let Pext = P – dP

V2
Neglecting infinitesimals of order higher than 1, we will get: w max    P d V
Vi
 WORK

Reversible Isothermal Expansion : wmax   (pex  dp)dV   (pdV  dpdV)

wmax   pdV  wrev

 dV 
Vf V 
when, p = p(V) and p = nRT/V for ideal gas w rev  nRT     nRTln  f 
V  V 
i  Vi 

Irreversible Isothermal Expansion:

Vf
wirrev   pex  dV   pex (Vf Vi )   pex ΔV
Vi

 wrev  wirrev
 WORK

Irreversible Reversible

Expansion

Irreversible

Reversible

Compression

•For a reversible process: Work on expansion = work of compression

(same path)
•For an irreversible process: Work on expansion (is less than) ≠
work of compression (same path)
 WORK

Irreversible
Reversible

Reversible

Irreversible
• Work done on expansion by the system on surroundings (sign
negative) operating between specified initial and final states and
passing through and specified path is maximum work available from a
system when the changes take place reversibly

•Work is a path dependent parameter, path function(so as Heat)

 Assignment
Ideal gas, closed system, reversible process
Calculate wforward and wbackward

isothermal
10 Pa, 1 m3, T 1 Pa, 10 m3, T

isochoric
10 Pa, 1 m3, T 1 Pa, 1 m3, T2

1 Pa, 10 m3, T
isobaric

isobaric
10 Pa, 1 m3, T 10 Pa, 10 m3, T3

1 Pa, 10 m3, T
isochoric
 Assignment

25 L of gas is enclosed in a cylinder/piston apparatus at 2 atm of pressure and 300 K. A 100 kg

of mass is placed on the piston causing the gas to compress to 20 L at constant pressure. This is
done by allowing heat to flow out of the gas. What is the work done on the gas? What is the
change in internal energy of the gas? How much heat flowed out of the gas?

• Po = 202,600 Pa, Vo = 0.025 m3,

• To = 300 K, Pf = 202,600 Pa,
• Vf=0.020 m3, Tf= ?

• n = PV/RT W = -PΔV Δ U = 3/2 nR Q = W + Δ

ΔT U

W = - P Δ V = -202,600 Pa (0.020 – 0.025)m3

= 1013 J energy added to the gas
Δ U =3/2 nR ΔT=1.5(2.03)(8.31)(-60)= -1518
J

Q = W + Δ U = 1013 – 1518 = -505 J heat

out
 HEAT TRANSACTIONS

In general change in the internal dU  dq  dw exp  dw add

energy of a closed system is given
by
- For dV = 0; dwexp = 0 and if dwadd = 0, then

dU = dq (constant volume, no additional work) =

dqv For a measurable change, U = qv

-heat capacity, C, the ratio of heat supplied to
the temperature rise it causes. C = dq/dT;
C = q/ T
-heat capacity at constant volume, CV = (U/T)V

-molar heat capacity, the heat capacity divided

the amount of substance, Cv, m = Cv /n. (unit: JK-
by -1 adiabatic bomb
1mol )
calorimeter
-specific heat capacity, the heat capacity divided
by the mass, Cs = C /m (unit: JK- 1 gm- 1 )
 Heat Capacity for Constant Volume Processes (Cv)

insulation T

Heat, Q
m added m

• Heat is added to a substance of mass m in a fixed volume

enclosure, which causes a change in internal energy, U.
Thus,

Q= U2 - U1 = ΔU = m Cv ΔT
The v subscript implies constant volume
Cv is a response function of the system. For a given quantity of heat, supplied to
TWO substances, lower temperature change will be observed for the system
having LARGER Heat Capacity
 Heat Capacity for Constant Pressure Processes
(Cp)

x
T

m Heat, Q
added m

• Heat is added to a substance of mass m held at a fixed

pressure, which causes a change in internal energy, U, AND
some PV work.
 Heat Transactions and Enthalpy

For dV ≠ 0; dwexp≠ 0 even if dwadd = 0, then dU ≠

dq
U = qp - pV qp = U +pV = U2 – U1 + p(V2 – V1)
= (U2 + pV2) – (U1 + pV1)

Define H = U + pV •Differential scanning calorimeter

•Isobaric calorimeter
dH = dU + pdV + •Adiabatic flame calorimeter
= dU - w (at constant p)
Vdp= dqp
At constant p, dH = dqp (constant pressure, no additional work)
- Heat capacity at constant pressure, Cp = (H/T)p
- Enthalpy change and temperature change, dH = nCp, m dT;
H = nCp,m T (if Cp independent of T)

⇒
Empirical expression,
Cp,m = a + bT + c/T2
 Heat Transactions

Therefore, in a constant Pressure process, the HEAT

withdrawn from the surrounding (>0) is equal to the
increase in the ENHALPY of the system

- for ideal/perfect gas; relation between ΔU and

ΔH ,
H= U+ PV = nRT
ΔH = ΔU + ΔngRT.
ΔH is the Enthalpy change occurring during reaction of gas molecules under
constant T and P

Example: 2H2 (g) + O2 (g)  2H2O (l) here, Δn = -3

moles

 ΔH– ΔU = – 3RT
 Heat Transactions
Variation of heat capacity over a wide range of temperature is given as:,
Cp,m = a + bT + c/T2 (Empirical expression)

 This expression for ΔH is perfectly

general and is valid for any
transformation at constant P
PROVIDED NO PHASE CHANGE or
CHEMICAL Rxn occurs.

In case of a Transformation where phase change occurs:

Example: Vaporization of liquid at constant T and P Qvap = Qp =
ΔHvap
Similarly, Qfusion = Qp = ΔHfus

Example: Calculate ΔH for heating 1 gm of ice at 0°C to vapor at 100°C under 1 atm
pressure.
since, H = U + PV

The fallacy in writing Cv is

differentiating
w.r.t to T at constant P we get
and
Joule’s Experiment Observation:
No Temperature difference of the water
before and after opening the stopcock.
1. w  0 As expansion into vacuum as pext =0

A B B 2. q  0 As no heat entered or left as ΔT =

0
U
dU     dV   U 
 dT
 V  T  T  V
(22 atm) Thus, dUT = 0 within the accuracy of the expt.
U 
dU   dV  0 Thus, under the conditions
Now,  
V
T
 T mentioned,
 U  U is INDEPENDENT of V
dV  0     0 U = U(T) Joule’s
 V T Law
 U 
Again from: dU T    dV; Now differentiating (dU ) Tw.r.t p
 V  T
 U   U   V   U   U 
       0
 P T  V  T  P  T   
 P T
 0 and    0
 V  T
For ideal gas
 Internal Energy and Enthalpy Change with Temp for REAL and IDEAL Gas

For any process

U  f (V ,T ) H  f (P,T )
U U
dU     dV     dT  H   H 
dH    dP    dT
 V T  T V  P  T  T  P
 H 
dU  πT dV  CV dT Real gas 
dH   dP  C P dT
 P  T
Real gas

Internal pressure
 U   H 
T    0 For Ideal gas    0 For ideal gas
 V  T  P T
 dU = CV dT (for ideal gas)  dH = Cp dT (for ideal gas)
From Joule Expt  U 
For ideal gas 
T   0
 V T
Internal Energy and Enthalpy Change with Temp for REAL and IDEAL Gas

U  f (V,T)
U
dU     dV   U 
 dT
 V T  T  V
dU  T dV  CV dT
 U 
T    0 Internal pressure
 V T • For ideal gas, πT = 0 because U
independent of molecular
dU = CV dT (for ideal gas) separation for volume changes at
constant T
For ideal gas
 U 
T    0 • For real gas,
 V T If dU > 0 as dV increases with T
constant, attractions between
Joule Experiment molecules dominate and π T > 0 If
dU < 0 as dV increases with T
constant, repulsions between
molecules dominate and πT < 0
U  f (V,T)

  U    V 
C p  Cv  P      
  V  T  T  P
 Adiabatic Reversible Process for ideal gas,
Cv independent of Temp

TV  1  constant
PV   constant
VT c  constant

T  P 1   constant
Example: Reversible Adiabatic Expansion (or compression) of an Ideal Gas
Example: Reversible Adiabatic Expansion (or compression) of an Ideal Gas
Adiabatic Irreversible Expansion of an ideal gas against a constant external pressure
 Numerical Problems on some Thermodynamic Cycles

For the Reversible Ideal Gas processes: Find ΔU,ΔH, q, w,

Path :

; ;
 Numerical Problems on some Thermodynamic Cycles

Path :

Path :

; ;
 Numerical Problems on some Thermodynamic Cycles

Path : ;

; ;

Path :

; ;

;
 Numerical Problems on some Thermodynamic Cycles

Now, compare path [A] verses path [B] + [C]

Path : Path

 Here we see from the calculation that the change state of an ideal
gas, operating through path [A] and [B] + [C], have the same value of
 Therefore, seems INDEPENDENT of the PATH followed for the
process and depends only on the initial and final state. And hence it is a
STATE functions
 Numerical Problems on some Thermodynamic Cycles

Now, compare path [A] verses path [D] + [E]

Path : Path :

We will discuss this term later while dealing with 2nd Law of Thermodynamics
 Variation of U with system variables:

U  f (V , T )

1. Change in U w.r.t. T at constant volume

  U 
Cv   ; q v  Cv T  U
 T  V
 U 
2. Change in U w.r.t. V at constant temp:  V 
T
For real gas
dU = CV dT (for ideal gas) As For ideal gas

3. Change in U w.r.t. T at constant pressure

dU  C dT  
U 
  dV  U   U 
v
 V  T    C   V  
 T  P v
 V  T
 U   U   V 
   Cv      where
 T  P  V  T  T  P
• Suppose we want to know how the internal energy, U, changes with temperature at
constant pressure
From: dU  πT dV  CV dT  U 
   π T dV  C V dT 
   
 T p  T p
 U   V 
   πT    CV
 T  p  T  p

• But the change in volume with temperature at constant pressure is related to the Isobaric
thermal expansion / expansion coefficient of the gas, α 1  V
α   or  V 
  αV
V  T  p  T  p
 U 
so,    π T αV  C V
 T  p

• Large α means sample responds strongly to changes in T

• For an ideal gas, πT = 0 so  U 

   CV (from definition )
 T  p
 Variation of V with system variables:
Experimentally known that the Volume of an isotropic material is a function of Temp
and Pressure

isothermal compressibility

relative/fractional
change of Volume
For an ideal gas : PV = nRT
coefficient of Isobaric thermal
expansion / expansion
coefficient

similarly T = 1/p

For solid and liquid  and T are approx.

independent of T & p
 Variation of P with System Variables:
Another quantity of interest which can be obtained from α and κT
is:
This derivative tells us how fast the pressure rises when we try to keep
the volume constant while increasing the temp.

Exercise:
How much pressure would be generated in a
mercury thermometer if we tried to heat the thermometer
the topthan
higher of the
the thermometer. Given: the
temperature where Hg, α = has
For mercury × 10−4 K−1 and κT = 3.87 ×
1.82reached
10−5 atm−1
We see that each 1 C increases the pressure by 4.7 atm,
about 69 lb/sq in. This is a lot of pressure for a
glass tube to withstand. It wouldn't take very many
degrees of temperature increase to break the glass
thermometer.!!!

Using a variation of Euler's chain

rule we can write
 Variation of H with system variables:

1. Change in H w.r.t. T at constant pressure

 H 
C p    ; q p  C pT  H
 T  P
 H 
2. Change in H w.r.t. P at constant temperature:  
 P  T
H  f ( P, T)
Alternately,
 H   P   T 
       1
 P  T  T  H  H  P dH = Cp dT (for ideal gas)
  H    T   H     JT C p
 P 
 
  For ideal gas
T P H T  P


3. Change in H w.r.t. T at constant volume:  H 

 
H
dH  C dT   
 T  V
  dP From earlier results
P
 P  T
 H   C   H   P 
  P    
 T  V  P T  T  V

 Variation of H with system variables:

This is zero for ideal gas BUT

what is this for a real gas????
H  f (P,T );
Cp
 H   P   T 
Applying Euler’s Chain Rule, we get: H  f (P,T) ;        1
 P  T  T  H  H  P
 H   T   H 
           JT C p
 P  T  P  H  T  P

 T  T
where,  (or, JT ) = Joule-Thompson, Coefficient    in this J-T expt.
=  P  H p

 ≡ dH    C p dP  C p dT
 The Joule-Thomson Expansion Expt

For ideal gas But for Real Gas

The Joule-Thomson experiment consists of forcing a gas at constant

backing pressure passing through a porous plug under adiabatic
condition and measuring the change in temperature.

The Joule-Thomson coefficient (JT ) =

 T  T
  
 P  H p

The most straightforward way to measure the coefficient is to

measure the temperature of the gas entering and leaving the porous
plug and divide the change in temperature by the change in pressure:

we need to decide what is being held constant when we take the partial
derivative.
In this case, since q =0, the change in internal energy of the gas is
equal to w.
 The Joule-Thomson Expansion Experiment

(Const High Pressure) A B (low pressure)

In this experiment q = 0 ; w = - p2 (V2 – 0) – p1 (0 – V1)

U = U2 – U1 = q + w = - p2V2+ p1V1

U2 + p2V2 = U1+ p1V1 H f = Hi Isenthalpic process

• The gas in A is compressed Isothermally under const Pressure P1 so that its

volume changes from V1 to 0. After crossing the porous plug, the gas in B expands
0 to V2.
• Boundary of the system moves with the gas so as to enclose the same mass of gas
 THE JOULE-THOMPSON EXPERIMENT
 T 
   
 p  H
If μ > 0 then this indicates
that the gas cools (-ve δT)
when gas expanded (-ve δp).

If μ < 0 then this indicates

that the gas heats (+ve δT)
when expanded (-ve δp).

The "inversion temperature"

indicates where on a (T, p)
isenthalpic plot the (dT/dP)H
flips from +ve to –ve. Or,
point where μ changes sign
from + to
– ve and the point is the
maximum inversion temperature

For a real gas µ is non-zero

(except at the maximum
inversion temperature)
 THE JOULE-THOMPSON EXPERIMENT
 T 
Joule-Thompson Coefficient ,  (or JT ) =    

 p  H
• µ can be either (+) or (-)
– Positive µ means dT is negative when dp is
negative
• Gas cools on expansion
– Negative µ means that means dT is
positive when dp is negative
• Gas warms on expansion
– Transition between positive and negative
µ is called the Joule-Thompson inversion
temperature
• Gases have both high and low inversion
temperatures
– Ideal gas µ = 0, T unchanged by change
in p on expansion G sa Tinver sion µ
(K ) (K atm-1)
• Practical applications:
C 2O 1 5 0 0 1.1 1
– Gas liquefaction
N2 6 2 1 0.2 5
– Isotope separation
H e 6 2 1 0.2 5
N2 and O2 will cool upon expansion at
room temperature, but He, H2 and Ne
will warm upon expansion at room
temperature.
 THE JOULE-THOMPSON EXPERIMENT

The Linde process

 Joule Thomson Coefficent for a van der Waal gas:

 T  T V T P V
JT   
  P H CP

,B ,C

where Z = Compressibility factor

Joule Thomson Coefficent for a van der Waal gas:

 T 
 T V T P  V
JT 
  P H CP
 Joule Thomson Coefficent for a van der Waal gas:

   T  Therefore, μJT depends critically on

T  V  T P V
JT     the constants a and b, which are
  P H CP the indices of non zero interaction
  1  2a  b  and finite volume of the gas
 JT  C  RT 
P   molecules respectively

2a
If ,  b then   0 (cooling observed )
RT
2a
If ,  b then   0 (heating observed )
RT

Inversion temperature
JT  0 w
hen T  Tinversion • If initial Temp (Ti) is below Tinversion
only then cooling is observed.
1  2a   2a  • And the final temp T2 is lower than
 0   b  o
r , 
   b T1
C p  RT   RT inversion 

2a
 Tinversion 
R
b
 Assignment: Derive the Following Expressions
For ideal gas
 P   μ JT 
1  H 
 
    P T
 T V 
Cp

 2
 T  T V T P V
C p  CV 
TV JT   
  P H CP

for ideal gases : JT  0

1  2a 
JT  C  RT  b 
P  

 H  T = - Cp JT
Isothermal Joule-Thompson Coefficient, T =  
 P T
Monoatomic ideal gas CV,m = 3R/2, Cp,m = 5R/2
 Expressions of some Response Functions

Property PD Value for Perfect Gas Info:

Internal  U 
Pressure T   
 V  T
T = 0 Strength/nature of
interactions between
molecules

  1  V   =1 / T
Expansion The higher T, the less responsive is
Coefficient its volume to a change in temperature
V  T  p

Isothermal 1  V
 T =1 / p
The higher the p, the lower its
Compressibility  T   V  p compressibility
 T

 T 
Joule-Thomson
Coefficient     = 0 Another indication of
molecular interactions.
 p  H
 Conclusion of Ist Law of Thermodynamics

• The internal energy of an isolated system is a constant

For isolated system : dU = 0; (as q = 0, w = 0» No perpetual
motion machines! )

• The energy of the universe is constant. ΔUsystem = −ΔUsurroundings

• When a system undergoes a process that leads to a

change of state then the sum of the heat q
transferred and the work w performed, is equal to the
change in the internal energy dU of the
dU system.
  q   w (Closed system, through a number of steps)

• A system contains ONLY internal

energy. A system does not containheat or
work.
 Conclusion of Ist Law of Thermodynamics

• Cyclic Process (Exact differential)

 dU

0

• In a cyclic process the work done by a system on its surroundings

is equal to the heat withdrawn from the
surroundings .
- δ w = δq
• For an Adiabatic Process  δ wad = dU ; (as δq = 0)

• For a Non-Adiabatic Process 

δq= dU − δw ≡ δq = (δwad – δw);
(as, δwad = dU)
 Conclusion of Ist Law of Thermodynamics

• The internal energy of an isolated system is a constant

For isolated system : dU = 0; (as q = 0, w = 0» No perpetual
motion machines! )

• The energy of the universe is constant. ΔU system =

−ΔUsurroundings

When a system undergoes a process that leads to a change

of state then the sum of the heat q transferred and the
work w performed, is equal to the change in the internal
energy dU of the system.
dU  q  w (Closed system, through a number of steps)

• A system contains ONLY internal energy. A system

does not contain heat or work.
 Conclusion of Ist Law of Thermodynamics

• Cyclic Process  (Exact differential)

 dU  0
• In a cyclic process the work done by a system on
its surroundings is equal to the heat withdrawn
from the
surroundings .  - δ w = δq

• For an Adiabatic Process  δ wad =dU ; (as δq = 0)

• For a Non-Adiabatic Process 

δq = dU − δw ≡ δq = (δwad – δw); (as,
δwad = dU)
 Appendix
Calculation of thermodynamic functions for various processes

reversible phase const p heating, no const V heating, no

change at const. T, p phase change phase change

w
 p dV   pV  p dV   pV 0

q latent heat qp = H qV = U

U q+ w q+ w
C V (T )dT

H q U + Vp
 Cp (T )dT