CHAPTER SYNOPSIS

0142025

Thermal equilibrium

g
 some Basic definitions in
Igmodynamiya
heat
aroscopic system

objective to
study thermo
studied
How do we determine the energy
Thermodynamics involved in a chemical
changes
change
what is the driving force of chemical process
To what extent do the chemical change proceed
I
Equideum
ThesmIcmer.ms

Surroundings
universe

The wall that

I_separates the system
from the surroundings
is called
i
Boundary

g The the whole

ofexperimental
small portion
universe on which
observations are done is called
system
 Boundary

Real imaginary boundary

wall or layer separating the
If the physical
it is called a real
system surroundings is present
the walls of a closed room
boundary Eg
If an invisible separation b w the system
surroundings is present it is called
an
imaginary
beaker where the beaker
boundary Is an open the
is the system the opening of
beaker has got an imaging separation

Rigid flexible boundary

If the dimensions are flexible
If the 1
dimension
Bagon
is rigid
walls of
a room

Diathermal adiabatic boundary

walls through a through

which heat can which heat cannot
pass pass

outerwalls of athermos flask

Cup's wall containing
containing hot tea
hot tea
 Elatiosfasystem

Iti
Surroundings peat Surroundings

I
me
didEmd
sn i
t.m n i.si m

Heat transfer
open system closed system
e.g yen run in an work Exchange e.g yen run in a
should always closed beaker
open beaker occur acronythe

Surroundings
Energy
maete
T.fi adiabatic wall
te.m i
isolated system

Thermodynamic Properties

Macroscopic properties Pressure P volume V1

mole n
muse m no of
Temp T density d

2 properties Those properties that obviously

Extensgy depends upon the quantity of the
matter of the system
E α m some integer fraction
e.g
mass moles volume heat internalEoru
energy enthalpy entropy
Gibb's free energy G HI

3 Intensive properties independent of the quantity of

I matter
I α m
molt
density pressure temp molarity
normality specific heat surface tension viscosity
refractive index mole fraction molar heat capacity
pH molar internal energyUm molar enthalpy molar
Hml
entropy molar Gibb's free energy Gm
Sml
NEB Mostly the ratio of two extensive parameters
are supposed to be intensive

state of the system

whenever the set of thermodynami properties
are provided with some values then they represent
a
statefasystem
eg
n modes Idea system
TI Pata v01 V1
Container wall
all the thermodyamic
whenever the value of one or

functions are changed then the system undergoes

a transformation from one state s I to another
state is II this is called Thermodynamic
process

n me
n mole
x atm
Thermodynamic Pf patm
P
v
T
Y L
ZK
process V5
14
Ideal gas II
s I

the change we
Depending upon the dependence of
into two
classify the thermodynamic functions
Categories viz

state functions Those variables that only depend

upon the the final state
initial
of the system not upon the path of change
21 press P Temp T Vol V U H S G

Path functions Those variable that depend upon

the nature of the path through
which the system has undergone the
thermodynami change
Heat work
19
what is
tooth
s chemical
Mechanical equilibrium
Thitilbrium equilibrium Chemical
Pinternal Pexternal
Tempsystem potential reactant

Tempsurroundings chemical
potential product

IerentthemdnamicPrcees
Isothermal process of the AT 0

1 2 A d 9 0

1 1 000000 2 d
finite infinitesimal
change small change
P isothermal
for n'moles of an

ideal gas at const tempt

Rectangular Boyle's law
hyperbola
x y C
V PV K n T const
Isobaric process If the AP or dP 0
p
Isobari

V
WO Isochoris process Av du 0
of the or

V
Adiabatic process
ΔqX
0 we only measure
can
transfer
or
Transfer the amt of heat
byn sys surroundings
dg 0
but we cannot measure
Tall the absolute valueof body
heat transfer heat content of a

cyclic process
where the initial final state
state sythem
of a
system

overall cyclic process

f For all the state functions
overall change in a cyclic
process is Zero
du dH dG 0
fods
cyclic
integral
 10 01 2025

Reversible vs Irreversible proteases

Reversible Irreversible
It is a multistep process It is a single step process

Quasi equilibrium byn No cam

each step exists
The process can never
110 of the opposing force
be reversed
is increased than the
driving force then the
process

can be reversed
very fast
process
It is a slow
very
process
Naturally occurring phenomenon
Reversible prolessel are irreversible
are merely an ideal
situation
 External press
upon the piston Pex

If Piston almost maseless

mechanical
almost frictionless earn Pext Pin
Vi ideal gas taken
Pressure Pin
cylinder Pgas

Letincrease the external press by some finite amount

so that there will be a sudden compression
realised by the gas the vol will change
from V is initial f final
Vf

Pf Pi
ext press
After sometime the
the pressof the gas insidethe cylinder
mechanical
come in equn
I will
again piston will stop moving
thus the
4 Effff Irreversible Compression

the press upon the piston

if we keep on increasing
by an infinitsional small ants say dp then
an eam to be maintained in byn the
WP can expect
system the surroundings reversible Compression
 Pext Pint dP

If

a thermodynamil System
Energies of
Internal Energy It is the sum of
all type of
that are present due to
E or u energies the system
the very existence of

Nuclear Bodergies
Edging
kinentgiest Potentifies energy

Proportifu
One can only measure the change in internal energy
but not the absolute value of V

UV UX

Vi
v01
U f T V T temp v

But for an ideal gas u f T

ideal AT 0
ie for isothermal processes on gas
ve
 Extensive property

state function

Um molar internal energy Intensive

How do we evaluate the AU for a system

Thermodynamic
SYSTEM system
Process

som amt of
Entergy Ui heat say 9 Entergy Uf
is added
i to the system
state state f
Up Ui 9

Thermodynamic
SYSTEM system
Process

som amt of
Ui work say
Intef
w
Internal performed
Uf
oins
i the system
state state f
Ui w
Up
was absorbed by system as well as
If both heat
work was done on the system then
 9 w
Ug Up

AU Δu us Ui
1ˢᵗ law of thermodynum

aamountwork
append

IUPAC convention for sign of q w

Heat absorbed by the system q ve

released by the i
ve
opposite
q
convention
work is done on the system co the in Psics
i
by a W ve

First law FLOT

of thermodynamics
conservation
Energy
universe is constant every
The total energy of the be destroyed
can neither be created nor

Of
isolated system is constant
The energy of
an
 Adiabatic wall

diathermal or thermally conducting

closed system

IIabmoutwkinmtherm.sc
Emechanical
work
PV To be majorly
non
work PV York studied in
thermo
P V work
Electricle
n

In
Pext

I set displacement
i or

if on the piston if

Let Avea of piston A

Force applied on the piston Pex A
work done PexXAXdx_
dw

dv infinitesimal
small vol change
extransion Expay For expansion
AV Uf Vi tue

Pex but for expansion

General w ve
formula i.e Av w follows
Compression workone opposite sign
refer ve
compression

FLOT AU w q
Realling
du 9 Pexdv

wait variance
In thermodynamics mainly study P V work thus
we
the area under the P V graph will always
describe the amount of work
done

work done for Gas

Isothermal integralstate
Ean of
Boyle's
law
PERT
 Lusible stormal Woon for idealgeno system
Thermodynamited ptoperty.to
measured
Process

enca en b en a

In E
Recalling the general
ean for work done

Idw Jex du since for reversible

processes Pext Pgas dP
nfinites.im Vi
small anthorn where dp 0

P MAG
Vf
Pex Pgas at
faw Pgas du
point of the
every
ui process
Totaldone Uf Also
Pgas

f
MRT
w
dy
Vi
w MRT
 In a 2.303
Wren iso NRT In
logises

Wreviso 2.303 NRT

log

0.301
5 0.699
log
2
log
0 477 7 0 845
log
3 log

log 8 3 log 2 0.9

wt for idd system

Irensibleystormal
Good ptoperty to
Thermodynamic measured
Process
be

for work done

Recall general expression
title for an irreversible
Idw PexTv process there is
no

eam in b w Sys
Wirr iso Pex Vf Vi Surrounding
Pex Pin

Wirr iso Pex

Pex
If
Pgas
If Here Pext will be a
constant pressure against
which the system will
Wirr iso PexMRT p either undergo expansion PexP
or compression Pex Pin
NEB
mentioned in the question assume that the
Ifnothing is
Pf Pex thus
P
Wirr iso NRT Ppt

1
Wirr iso NRT 1,1
Graphical Context of Reversible Irreversible
vs
considering isothermal
process
expansion compression

Isothermal expansion
mm mm
material is ideal gas
working

Ilestep expansion

irreversible
pPi
Pf Pi V27

lt In the irreversible
process the work done will
Pf 2 always be done against a
fixed final prese Pf
V1 a
irreversible
two steps expansion Wtwo Wsingle

PPI get

jii.fi
V V2
 multiple step expansion

B P dp
d'Pz
B P2
pP i
Pu Ps dB
P2
Py dPu
ps
i

II fiii
i.fi
E
aamsum

Infinite step expansion

reversible

Wren expansion irrevt expansion

P
t
For expansion
alone
I
f
Vi of a

Isothermal Compression
mm mm
single step compression

image
ppf prior
i
i ippp

I i
pit f I
gijy.it
Pf
g p
2

of v V1 v

Two step compression

Wtwo single
pps
ti.iq

i it ii
V3
V1 y

compression
Multiple step
 Wmultiple Wtwo
p's
f
IIIi
B

Vtia is
it

Infinite step compression

P
it Reverssible step

in
f
vi of y
Vf Vi
g

win Wren compression

ideal gas at TK
 Convent
fdwcrev.is

whiff
ideal gas at TK

us
T.in
pression fdw
irrev iso 0

Idea about Earth

mym
T
form of
energy
which
influences the temp change
of the system
absorbed
remitted
by heat
by system
q ve ve
q

Epecific Heat Capacity 1

 13 0120.25
spontaneousprocess

Ecycteria
what is a spontaneous change
irreversible process and be
It
reversed
is an
may only
by any external agency
y g of
thermodynamics
SLOT
Enthalpy of ryn

ΔpH Enthalpiesproduct Enthalpies Reactant

dont
Eins c

I TYE.ve
endothermic µ

coordinate
Nael aq Not109 color
tue AU nCv mB
Ault
Spontaneous
change AH ncp.im
In the forward direction
the degree of randomnell
increases i.e entropy s which makes the process spontanan
What about the processes where ΔH 0

Acg valium
9
spontaneous
diffusion
volume of occupancy for the gas molecules
thus intermolecular distanie so the degree of
randomness Entropyt Driving force
Mathematical definition of Entropy
Reversible change at temp T K

Fantaabsorbed
heat is
State I
state II
for a system for a system

dogs 19
change
in entropy
of the system

dssus e

Properties of entropy
It is an extensive property
It is a state function
 i.e whether we out the process in a
reversible or in
carry manner the
an irreversible
Assys or Assys would not be affected
dssys
T Issys IS us
i
fire dosis
measured
Absolute value of entropy cannot be
only As can be evaluated
It
unit of s
caik or ergk
unit of Sm TK moi
malypy

Intensive

AS Assys Assurr
total

Universe
a system would also
For any change happening in
affect the surroundings unless it is an isolated system
For
any spontaneous change AStotal 70 if the

entropy of universe reaches maximum

value for
any
certain change in the system an equilibrium will be
established where True for any
fastest reversible process
Different mathematicallationsytopy
dogs Yes
darev T dSsys
Now recall FLOT
AU 9 w
be reversible in nature
how
assuming the process to

du dw Pdu
dq Pdu

ncymdt Tdssus Pdu

52
ncu.im I dssus Idu V2
2

fdssus ncu.mg 1ffecafEJasy

S
T Y

ncu.mn nRen
Assy f
Similarly
dH du d Pv

nCpmdT dq Pdu Pdv udp

nCpmdT T Issus VIP

 ncp.im P
Idssus
S Tz P2
Assuming
fossus ncr.mg
thegas
S T P

Assys n Cpmln
MR M
F

jyfrm.istormal T T2enE
ncym Assys
E
o
nren

Assys ncp.mn
nRln
1
Assus nRln

NR In
F
nren
E Isothermal

If the process is isoburic

thentkecordingt eqn2 ASsysencp.m
ln nRln
1
 i Assus ncp.mu E Isobaric 4

process is isochoric v V2 then according

If the
to ear

ncu.mn nren
Assy 2

ASsys nCymln Isochomic 5

change in entropy calculation during the

s 1 G
phase
tfomationfireisobaric
ds 1141
dye This can be performed
by providing Latent heat at const
press temp
AH
L phase
transformation
ΔvapH
L G
Afu Asuba
IS L sea
For S L

Astusion
Thts freezing pt e.g
27
k went

For 5
Gsp 11H
 for L G
Asrap 1H
S Reactants
Aspen I Sproducts

Isually particles upon a chemical

say if of
we the no
iniveases then entropy Also upon a chemical
rin if the no of gaseous particles then entropy

ax Nazcos 9
Cyst1
2 Nanco
G

b H2 1g H 19 An _of p'des
get
Eels 31219 Fees
no of gaseous molecules
AS ve
Cds
N2 91 34219 2MHz 18
2 1 3 2
Agn
no of gaseouspiles
i AS ve