LECTURE NOTES

&
VIDEO LECTURE LINKS
By -
ANKIT GAUR
( IIT - BOMBAY )

Complete Playlist -
https://youtube.com/playlist?list=PLDhC71P3Fpuq9eSS2KVP_kXp69O9Kr_PC

Lecture 1 - https://youtu.be/0xopOuE-3E0
 “THERMODYNAMICS &
THERMOCHEMISTRY”
It the branch that describes the
is
of
matter and
science

behaviour
of
the
transformation between the
different
scale
forms of energy
on a macroscopic .

between
energy transfer
It deals and
surroundings
with
system and

helps in
predicting the
feasibility of the process .

Terms
Thermodynamics
used in :

System : The
part
of
the universe which is under
enperi
mental observation

Surrounding : The rest

of
the universe around the
system is known
 as its
surrounding .

Universe System Surrounding

i. e = t

Types of systems :

① Open A which
System :
system in
enlarge of
matter and
energy
take called
can place is as an
open system .

② Closed System A
:
system in which
cnchange of energy can take place

but the en
change of matter notis possible .

③ Isolated System : There is no en

change of matter or

energy
.

④ Adiabatic system : A
system which does not allow the
enchangeg
heat matter but the
or en
change of energy
in other
forms like work

Such adiabatic
is
possible .

systems are known as

systems .
§ Categorise the
following into
different types of systems :

( is A cup Open
of Tea →
.

Cii , Camphor →
Open .

Ciii ) A cop
of
Tea covered
by a
plate →
Open .

Civ) A sealed bottle cold drink → Closed

of
.

A sealed Closed
bag of chips →
.

( vis Universe →
Isolated . WILT
closed f f
A ncentainer movable Adiabatic
Lvii ) with
piston and
perfectly → An a
.

insulating walls .

used
( viii ) A perfectly rigid container with
perfectly → Isolated

insulating walls .

nX
Adiabatic walls : Boundaries which do not allow the en
change of
heat
energy
i. e
q=o {g - heat
enchanged }
Egf walls
of
a Thermos
flask .
Diathermic : Boundaries heat
which allow
enchange of across

them are called diathermic walls .

Container
Egf walls made
up
of copper ,
steel ,
iron etc .

State variables / state functions : Variables required in order to

defineState
state state
of called variables
a
system are .

variables are
only dependent on initial and
final state
of
the
system and are
independent the path
of
taken .

Path / Quantities
variables Path
functions : which are dependent on the

achieved
path or on the
way
the system has a
particular state are

called path functions . These quantities are

defined when there is

involved
a
process
.

§ Classify
P
the following into

→
path
state
or state
functions ( variables .

cis
T → s
 V → S
Cii )

( ID Displacement
→
S

RE dueler s
X
gravity
→

( H) s
( vi)
Enthalpy
→

( vii) Internal (Ecru )

→
s
energy
( viii ) Gibbs free energy (G ) → s

S
( ix )
Entropy Cs ) →

(x ) work → path

(xD Heat →
path
Lxii ) Path
work done
against fiction
→

(xiii ) Distance →
p
dim Heat
→
P
capacities .

NITE : i) For a
cyclic process change in slate
fund must be
zero

§ die = o
where * = state
fear
 Lecture 2
Video Link
https://youtu.be/78nV9MhYJkk
 ii
) Change state
in
functions are not state
functions are not state

functions They
.

definite are quantities .

etc
Eff AD
DT DP AV AG AH du
.

g , g , , ,

Intensive & Extensive Properties

Entensive :
Properties which are dependent on mass or
size
of
the

enknsive properties additive

system are known as .
These are

in nature .

Intensive Properties which independent

; are
of man or
size of the

system are known as intensive properties . These are not

additive in nature .

§ Classify the
following properties into intensive and enknsive :

Property (III)
 Vol E I
( i) .

xig Temp .

ID Man E xii, Pr .
I

iii, Moles E xiii, cone . II

iv) Resistance E xiv)

pH I

Total heat
v ) capacity E xD
Boiling point Z

internal Point
vi
) Total energy
E xvi)
Freezing I

viig Total Enthalpy E xvii)

Vapour Pr .
I

Gibb 's Free

Viii)
Energy E xviii)
Resistivity I

Molar Heat
ix)
Entropy E xix,
Capacity I

× )
Density
I xx , specific fleet
capacity .
I

8-
'
F-

h/2 42 uh
V12 I

① ⑨
IOT ④
I
Nio Any of something
unit
( is enlensive
property defined
when
:
on
per
to obtain another resultant
property of the
system ,
the

intensive
property will be in nature .

Man unit vol moles unit vol

Egf f =
per
. care
k
=

d
per .

↳
{intensive ) @ tensive) ( intensive ) ( enknsive )

Ix E = E

de

⇐
, = I

THERMODYNAMIC EQUILIBRIUM : when there

change in
any
is no

observable or measurable
property of a
system with time
,
then the

system is said to be in
thermodynamic egm .

A
system in
thermodynamic eqn consists
of :

1) Mechanical Egm .

2) Thermal Egm .

3) Chemical Egm .
 Processes
Types of Thermodynamic
( on
:

state )
of
the basis or condition .

Any process by
which a
system can
change its state
from one

thermodynamic egm to another state

of thermodynamic egm is

said to be a
thermodynamic process
. There can be
infinite types of
thermodynamic processes
out ,
of
these a
few important ones are .
.

(a) Isothermal process : T = constant

IT O DT O Ti Tf
= = =
, g

(b) Iso choric : V constant

process
-
-

DV O DV O
Vj Vf
= -
=

egg
-

(c) Isobaric process

: P = constant
DP = O
g
DP = O
g pi =

Pf
(d) Adiabatic heat
process :
enchanged -
- o

i. e Q -
- O

dq -
- o

(e) Cyclic process : A

system which
undergoes a series
of changes
and comes back to its initial stale ,
then this

type of process is known as a

cyclic process
-

variables
change in state in initial and
final
state in such will be i e
processes zero
. -

DV -
- O AT = O AP = O etc .

, ,

§ Consider taken
a
system for which initial readings were

hours
CP v.,
T )
then time
at t o

after very long t 120 another set

-

a
-
- -

ofsaidreadings were taken CP v.,

T) .
Which
of
the
following can be

with
certainty for the
system from above observations -

i) DT -
- o Iv) DP = o vii
) T -
-
const .
 ii du o Ty AV o viii
, P const
)
- - =
- -

iii ) DP
-
- o Ivi, DT -
- o in, V= const -

Convention Heat
IUPAC
Sign for
and work

Anything
taken
which

to
increases

be
the internal
energy of
the system
is
positive
work Heat
= I

wgglgemdenemlhe
w
Eve ) ( tue )
Q →
Heat to the
given
system

bathe
wingmen
y
-

eve,
wa
eve ,
the
given by
Heat

to
system surrounding
 Lecture 3
Video Link
https://youtu.be/ANZ1Qr8B7AA
 Modes
of Energy Enchange
A
system can interact or
anchorage energy with its
surroundings
commonly by the
following two
ways
:

i HEAT
)
iij WORK .

(1) Heat : Keat is

defined as the
energy transfer across a
boundary
between
as a result
of temp .

difference system and

surrounding
Heat
may
be
transferred through the modes
of
convection ,
conduction

or radiation .

( II work : work calculation equation :

K dx
- →

T T
Area -

-
A
{ Gas I
=
I
I
-
I
← Pressure =P

Vi = Ax Ls
vital At
Vf = La
 -

.
-

dw -

- F. ds
-

i .
dw = P A. dm
.

fdw =
ftp.A.dn
]
{ }
is added to maintain

=u
sign
-
ve

W p the IUPAC convention

sign
.

for work done in

chemistry

(a) Reversible or Quasi static Process :

In this
type of process ,
the system is
always in thermo -

dynamic egm at
every stage of the process
Each intermediate
-
.

step in in
thermodynamic egm .
An ideal reversible
process will take

time
infinite to This
get completed Palm
Pent
.

type of process can be drawn

I
-
-

P V
graph
on a
-
.

1111111111111111

Vi
{ ," ,

Gas
, "

gu,
 ^

9
Af ago

:#
- - -

Pent Pin Idp P

"

: = .

i
'

Vf :

w
fpentdv
-

: -

-
-

Vi Vf
pi
•÷
- - - - - -
- - - - - -
. . .

f (pin
'
i W -
-
-
Idp ) du ; ,

is
. .

Yi
:D
°

w -

pi .

±I'
Vt
w = -

fpindv
Vi

En For an ideal isothermal Pin const

nuR
in an
process
: T
gas ;
-

= -
.

Vf Vf

fnrj fd
i

- -

W = -

.
du - NRT

*
Vi
 W = -

NRT
(luv ]!!

tuff) leg (VI)

W -

- -
NRT = -

2303am

Q A substance is empaneled from ( 3ms) b- (5ms)

against a variable

lots then calculate

of
v) Pa the work done
during the
-

pr
.

process
.
( Aus in SI units ) .

5m3

Soi
=
: w = -

Spent . dv
3ms
5

= -

f@ t5v ) du
f- ( OV
+5212) ) ,

(
51¥) ( )
) (
W ? Nlm '
5×235
= -
50 t t 30 t m

w = -
60 J bus
=
 Work done the
on
system = 60£
-

Work done the

by system
= t 6008

NOTE Area under P V the done

graph gives magnitude of work
-

: us

in the
process
.

(b) Irreversible or
spontaneous or Natural process :

If a
process is carried out in such a manner so that the

system is
thermodynamic
in egm at :

initial and the but not at intermediate

Ci )
Only final of process

stages .

Ciii At some
finite no .

of
intermediate
stages along with initial and

final state .

Irreversible time It cannot be

get completed finite
will
process in .

drawn P
diagram All real irreversible
V
on
processes are
-
. .
 palm -
Pent = Pin ( )
-

Pi
gas (
-

gas )
-

n
11177 l l l l l "

Pf
l l l

god

{
- -
--

.it?bqy=Dent--Pfcgas
,i¥*¥ fat , i
Vi me , ,
;
Gas I
pi - - -
I - - - - - - -
-

&
i
"
Vf G >

fdw
Vi
Spent dr Vf →
-
i

-
-
.
-
.

Vi
-

.
'

Pent -
-
const .

W pent fdv Pent ( Vf Vai )

'

.
. = -
- -

win = -
Pent ( Va -

Y ) =
-

pent DV

conversion : IL - atm = 101.38

I L -
bar = 100 I
 Lecture 4
Video Link
https://youtu.be/Oz5VtNViwDU
QI Work done
during the enpansian
of a

gas from 4dm ' to 6dm '

against a constant ent .

pressure of 3 atm is
?

0=2 Consider a
cylinder of uniform
cross section in which an ideal
gas
is

held
filled
at 300K .
The
piston is
initially by a stopper .
Find

out the work done the stopper removed the

if is and
piston
allowed (
is to empanel until it stops by itself given Palm Latin)
-

: -

Lahn
Palm =

T -
-
300K = constant

am
"" " ' e , , , FE
Vi =

to
IL
atm
f
Pi =

Vz

Soi z
w = -

Spent du Pent -
-
const -

V
,
 w -
- -

pent ( Va -
Y )
= -
3 atm ( Gk - 4L ) { LAMB = IL }
w = -

G L - atm

W = -
G x lol 3 .
J

w = -
607.8J Aus
=

f )
SEI :
pent -
-
Palm -
-
Latin ( pi ) = loath Vi =
IL 7- const
.

gas

i.
PEE Fenster, -

fridges -
-
sam :
y
-

- 102

= -
Latin ( vz -
V
. )
-

-
-
Latin ( 10 -
1) L

w = -
9 L -
atm

W = -

9×101.3 IT

.
: W -
-
-

911.7 J Ans
=
 ideal
E L mole
of an
gas undergoes enpansian process from IL to

10L
by the
following given processes :
i)
Against a constant ent .

g
pr
- Latin

Empanels to Pent
ii )
from IL 8L
against constant satin and
-

a -

Pent
feoffee to 10L
against a canst Latin
- = .

Then
nthe work done in both the
processes separately .

Soi : i
, w = -
pent ( vz -

Y)
= - Latin ( co -
I ) L =
-

B L -
atm Ans

ii) w W
Total
=
, two
= -

pent Cv ,
-
v
.
) t
f -
't
Pen Cuz -

vz ) }
= -

5 (8 -

I ) t C -
I ( lo -
8 ) )
= -

35 -
2

= -
37 L -
atm Ans
=
 "
Law (2 LOT)
of Thermodynamics
Zero
If two thermal the third
systems
with
are in egm system
the thermal
separately then , all three
systems must be in

with each other

egm
.

B TB
TB =

TA
"
Te
I §
A C

then IT =
Tc

( FL OT )
First Law
of Thermodynamics :

It is based
"
theon
principle of energy
conservation .

According
to this law Total isolated
system
energy of
an remains
,

conserved ,
but one
form of energy
can be converted into another

form of
'
?
energy
If a
system is
initially in a
particular state with its

total internal CE , ) and amount heat

energy as
( q) of is
given
te the done
system along with Cw) amount
of work
being
the system the total internal becomes (Ea )
energy
on now
,
.

then Ez = E
,
t
q t w

F- E BE or DU
q tw
q
= =
t w
-

a ,

INTERNAL ENERGY : It is the sum

of
all
forms of energies
( like Translational K E Rotational K E Vibrational KE Bond
energies
.

, , , ,

electrical e*e )
magnetic energy , energy
. - - - -

It out the absolute value internal

impossible find
is to
of
but the internal calculated
energy change in
energy
can be .

DU w
q
= t

For ideal P work is isobaric

only
an where - V involved in
gas ,

i. e v const i. DH O
process e
- -
.
-
-
 dw
Spent dr
i

- .
= -
- = O

W
'

O
-

-
. .

Heat
Du
gu enchemged at const Vol
'

.
.
- = -
.

DU
'

. .
=

of = n CAT
,

or du cu DT
q
= = n

§ Find out the

change in internal
energy of
the system which is

heat does
supplied with loot
of energy
and it
simultaneously
23J work
of
.

fast
Solh : W 235 Woes =
-
23J

÷:÷÷
-

*
-

.
: : :::
DV = too -
23 DU = 100 t C -
23 )

-
i

.
DU =
77 JJ Aas du = Coo -

2$ bus
= =
Q A system supplied with 1 KJ Heat and it
simultaneously
of
is

empanels flan L L to 3.23 L under an enter not pr .

of
1bar .

Find out the

change in I. E Cu )
of the system .

SII

}
I 7%1?G.
:

as su t du

foot?
-
-

= -
2.23 L -
bar -
22333
w = -
2.23 x too J = -
223 F D U 77¥ J bus
=

Calculation
Heat
of Heat :

calculated
is
path June
and is
generally indirectly using
-
a

1st law Heat

heat capacities
of thermodynamics .

enchanged is also related with

and BF .

( is Total heat (G) heat

capacity to
: It is the required raise the

temp .

of
the system by Csec ) under the
given process
conditions ( Eaten sire )
.

prop .

call
mathematically Cp doe Jfc 51k
-

: = or or c . .

DT
 dq -
-
Cpd T
q Tz

1dg ! Gd = T ( If GT is independent of temp .

)
then

/ q = C AT
#

Lii ) Molar heat (c ) It is the heat the

capacity to
:
required raise

temp of Linde the substance ( intensive )

.

of by 1°C .

prop .

mathematically day I
' '
i
J mot Find
- - -

K
-

: C = or e
n DT - "
'
Col
-

nd K
.

or .
.
-
- -

CDT
dq = n

both sides ( C is
independent of letup )
integrating
.

: .

q = he AT

Cp : Molar Heat
capacity at const . Pr .
 Lecture 5
Video Link
https://youtu.be/IwERpIcRtjU
 (✓ Molar Heat at
8
capacity const .
vol .

for an ideal :
Cp G R
-
-

gas
-

CI -
-
F G =

Rr
-
I

Heat Heat required

Ciii )
Specific capacity (s ) : b- raise the temp .

dy
unit mass
of
a substance
by 1°C is known as the specific
heat the
capacity of substance .

S dq l I
Jgm
-

K
-
=

Tdt

dq = m Sd T C
,
= n C = ms

or Q = ms DT
Note For isothermal processes like
melting or
boiling ,
the heat

capacities will be :
G A
Cp S because d T 0
-
= = = -

WORK DONE IN VARIOUS TYPES OF PROCESSES :

① Isothermal Process ( DT -

-
o ) :

For an ideal
gas :[ du = n Gd T = o ]
.
: du -
- O DU -
- O
Change in internal

is
energy zero
.

for reversible isothermal process :

W NRT du
(¥) under P V
-

graph
area
-

=
- -

for irreversible isothermal

pent
process
DV
:

Pent Cv y)
wiry = - = -

,
-

§ Compare the
magnitude of work done in reversible and irrever -
 si ble in
processes
- :

Enpansionn
Ci ) Compression

SOI :
Single stage irr . Vls reversible

p
Iwrevl
- -
o
. - - -

, .

:/
'

il
'

twirl = I -
Pent Cra -
Y ) /
'

i
in: T.ca.us ,
r .
. . . .

i :
>
V
,
Vz

( Wrevl > twirls .

step
 2.
Step irreversible process :
^

P - - - - - o
.

:÷
it

÷¥÷i÷÷¥i¥÷
"
'

P' Cr
HI =/
-
v.

✓ 191--1 Pack - v. YT f
✓
>

twin lamp I Wil that ID

'

- Iw I ,
(v ' -

v.

( Wal = Ipa ( Vz -
V)
'

Iwm ) > twirl a steep > twirl step

On the
Tsing the no -

of steps in irreversible
process magnitude of
work In obtain
of
increases case co step irreversible
process we a
-
.

reversible
process .

( wow I > . - - . - -
-
twin 13 -

sup
> I win 12 -

step
> / Wint
, -

step
or

twirly -

sup
( For cnpansim )

( in 6min :

n
twirl,
step
=/ Pack -
v
. ) )

tiiiiii :
i.

"

>
-

V2 -

Vil
 vill
ftp.cv
'
-

^
"

÷i÷÷÷i¥¥÷÷÷÷÷÷I
"

twirl twin ! twirls -71

'

Wiggles
- i

> > > - -

- - -

step
- -

sup step
step
-

,
-

-
-

( compression ) lwreul

Note @ in) (wir ( Wirtz ( )o

Wrenn
> > >
step
- - - - -

2. step
- -

step
-

step
-

, -

( with sign ) (feeling Cwrev )

ogppznss.im )
.
 2 moles ideal undergoes isothermal
§ of an
gas enpansion from
to at Then calculate
IL 10L 27°C . max .

possible work that

can be obtained
from the
system . (Hint :

lwrevlenpansian ) (R E) -

* A
SII :
lwrevlenpansim is max .
V
,
= IL Va = lol

T = 27°C or 300k n = 2

lwreul
k⇐ )
i -
=
n RT

100
= 2x x too t 2.303
leg (tf ) J

= 50 t 230.7 J =
11515 J AIS

② Adiabatic Process (Q -
- o ) :

adiabatic
flan ist Law DU
:
9=00 in
i '

qtw
= .
an

process
I .
DU = W or dU = dw
 feign : du nerd -1 or du n GAT
-

= -

)
diabetic : dw -

nerd T or w -

nerd -1

panacea
. - -

Q What
.

( cu )
is the
final
that
temp .

of
oil mole
of
monoatomic ideal

work
gas
IR
-
-

perfumes 75 calories
of adiabatically
temp ? ( R 2 Calmed K
' '
)
-

the initial
if
-

.
is 227°C -
-

(a) 750k (b) 35012 %) 250K ( d) 150K .

Solh : adiabatic du nest (ideal

gas)
w
i -

q=o
=
i
-
-
. .

.lk#R)xlTz T.
)
w -
-
o -

75cal ( Ta )
to 3*+21×61
= x -
500k
+
-

75302
-

= Tz - 500 Tz = 250K

-
250 = Tz -
500
I
 Lecture 6
Video Link
https://youtu.be/WmmQAkuUpo8
 (a) Reversible adiabatic Process :

! 't
for ideal Piv
an on

gas
: '

zf purr cast ①

{
= . -

r -
s
TV const
for ideal RV NRT
- -
= an
gas
. -
-
.

P ②
TI
" " -

'
rt !
-

p canst .

②
Using ① d

f-
If ( ur)
Type of Cr Cp
nR
const
= .

Gas " '

T.LV) const
Monoatomic
IR IR E
-
-
I. so
=

Ing =

has
leg : He ve)
,

Igi::÷ .ir ¥ at::ii:3

" "
.

Linear
Polyatomic SIR ZI R
¥
14
-
-

(
Eg :
Co2 ) 0=2--0
@ near
)
linear
31=1.33
Non UR
IR 3R
-
- -
Eff (Nhs ,
Chu )

for a reversible
process
: w
f Pind V
-
=

for adiabatic
process
: P .
Vr -
-
K

P = K

J
i .
W = -
dr

[ I ]!
Fdr
s
-

= -
k v -
k

T
-÷rcrEr
' -

i. w ri
-
-
-

C :
'

PV ! K =p
, y
? prig
? r
leva Kui ]
' -
-

w -

-
-

w
-

-
¥_p v.hr J , .
' -

r -
s
 Wren =
Pzvz -

P V
, = DI
,

E r -

(b) Irreversible adiabatic

process
:

adiabatic & du
'

w
-
'
-

q=o
. . .

Irrevesible .
.

.
W = -
Penta

{ G=¥z }
ideal
for an
gas
du =
nerd -1 where

Du
- .

. = W

I .
ncv AT = -
pent AV

( ez ) ( Va )
if
n .
-
T. = -
pent -
Y

(nRp÷ nrp÷ )
( Tz Pent
.r÷ )
n
-

T =
-

x¥
( Tz T ) Pent XX
( If ¥)
-
= - -

-
 arent
# ¥)
-
-

mole ideal monoatomic adiabatic

Q One
of an
gas undergoes
irreversible
compression from Latin at Sook to 2ohm
pr
.

against
enteral calculate
of
a cast 2dm Then
pr
.
- .

C) Final temp .
( Ta )

Cii AU ( ans terms R )

of
in
,

Ciii , work .

y
#
r
Seth:( is
for monoatomic
E
: Pent
'

:
-
- -

gas
- =

Pent = 2 atm

CTz-3oo)T
Pz
z
Latin P = Latin in
2µg 3g)
-
= =
, -

=
? T
,
= 300K E -
L

X(
tf) T2-z
-
=
 Goo -
Tz =
3Tz -
Soo
-

1200 3 Tz 900 2100 5- Tz

272 =
-
-
=

T2 = 420k Ans
=

di du ng DF It R ( Tz T ) ( 420 )
IR
300
y x
- -
-
-
= . =

r
'

.
Du -
-
180 R Inc
=

Ciii adiabatic du 180 R

tus
'

W
-

,
-
=
.
: .
-

Comparison between reversible Isothermal

,
adiabatic
and
Poly Tropic processes
:

i For isothermal process : P V const

)
-

- .
.

adf.ir
t p .

I = O
dare =
-

I
 Vr
ii
) For adiabatic process : P const
- .
-
-

r
adud
-

For
iii )
polytropic process :

}
p.vn = cast .

{ where n 't I
,
I

dad (f)
{ tsf
}
n
Cp Cr
-

= -
-

Comparison
for enpansicn :
for compression :

:÷i÷÷÷÷÷÷
^ ^
"

:÷÷÷÷
q

i
'
"
i

: ✓
>
→
>
.
 I
'

l
l l .

N
l l l

action

µ§↳
l
l
l
l

P
l

pAk
i
l
l
l
l
l r ,

l
I l
f
T l l

'
'

J '

I
, I l
'
I
,
adia
i
pv ! K

i
i
i
t
t ) ✓

E A
fixed
amount
of an ideal
gas undergoes volume cnpansion
upto
'
scene
final
volume
by the
given processes
:

}
( i) pv = cast -

the
magnitude of
Cii , D. v const Then work in
compare
-
.
-

't
Ciii ) P -
v = cast .
these processes
:

"
Civ ) P -
V 2
= canst .
Goth :
n l l
=
p '
I
•

!#€
p l l
,

pv
'
'
.
.
cast →
Ciii )
→ max area
uyideere
canst → Cii )
pr =

I '
pv 's const →
(i v
)
l
=
l

t min area under the

pv ? cast (D
'
→
.
→

l curve
I
.

I >
✓→

lw.IS/walsIwulslw . I
3 >

{ with

}
2 > 4 I 3<2 L h C L
sign
> :

due to
inequality reverses
sign
-
ve

work done
of
(H )
Enthalpy
we knew that heat
enchanged at const .
vol .

Cq ) = Du
,
but most
 take place at const
of the
i
chemical
at const
reactions

1st Law :
.

pr
. conditions .

pr
using
. . .

DU
qp t w
=

: P const W PAV
-
.
- . = -

- . .

Du PAV
qp
= -

DU t PAV
qp
=

U2 -
U
,
t D ( vz -

Vz )

qp =
@at Pvs) -

¢ ,
t PY)
-

(H)
enthalpy
: .
We
define a new
thermodynamic quantity enthalpy Cn ) such
that H -

-
U t PV

H2 H H tensive
property
An
qp
→
'

. .
= -
= en
,

also is a state
funen .

Heat at cast Pr
changed
DH
en
qp
-

.
.
-
=

for an ideal
gas gp
= n
Cp AT = AH
 Lecture 7
Video Link
https://youtu.be/JjFK5UCAJmU
 tf Ut PV
.
-

. =

also ( relation )
DH DU t DPV
general
-
-

at const .

pr
.
condition
DH = DU t p AV

Q A certain mass
of an ideal
gas
absorbs 88 KI
of
heat and

is
simultaneously compressed from Io L to 2L at a const -

pr .

calculate values
of 25 atm Then
of
DH and do
q
w
g
.

for the
given process .

Solh :

q
= 88 KJ (at const .

pr
. conditions )
=

qp
= 88 KI = AH Ang
# q
& dm )

const
' '

pr process
.
. .

-
'

.
W = -
pent su

= - 25 (2 -
lo ) = 200 L - atm = 200×101.3 J III
=
20260 J = 20.26 KJ
 1st law
Using
'

-
.

DU 88 KJ 20.26 KJ
qtw
= = t

- : DU = 108.26 K J Ans
=

Q2 ideal empaneled
mobs
of
an
gas
is
isothermally and

reversibly from calculate

'
4dm to so dm
'
at 27°C .
Then

(Aus )
DV
g
DH g
w and
q for the
process . in unit
of
Joules .

Seth fee ideal du cud T

:
an : n
gas
-
-

DH = n
Cpd T

: isothermal : . dT= O

f :: : : %::3
'

.
.

isothermal reversible : .
w = - NRT link
v
,

100
w = - 2x
x
# + In
 W = -
50×100×2.303 (leg lo -

leg ) u
(leg
=
2 -
-
O -

3)
= -

5×2303 x ( I -
2x
leg 2)

@ 4)
= -

11515 x -

w = -

4606 J Ans
=

W = - 4.606 KJ

-
: DU = O

i
'
t 4606 I
q
w
q
= -
. . =
.

or t 4.606 KJ
q
±

NOTE : is § DH -

- O
{§ →

cyclic integral }
ii) H Ut PV
-
.
-
-

DH
'

- . = d U t Pdu tvdp

iii
) For a chemical
process
or
for physical change a
at const .

pr .

and temp .
conditions :
i

.
'

du -
- do tdpv
 { }
& AGV ) ⇐

Dng RT where
dug
=

change in no .

moles
: DH
of of gases
angry
-
= but

§ A mix .

of
2 moles
of co and Linde
of Oz in a closed

vessel
ignited to get Co2 If DH
is the
enthalpy change .
is

internal
and DE
change energy then
is in :

i
,
Ah DE >
SIM 20cg 02cg 202cg ) :
,
t
,
→

ii) DH = DE

Vidi ) (2) (2+1)

SH L DE
Dng I
-
=
=
-

w) None the above

of
AH
.

.
. = Au -

IRT

Dh L DU
'

. .

Q For a
gaseous
reach :
Acg ) t 3
Beg ,
→

3cg ,
t 3D
egg
DU at R 2cal I met t
the
-

17 kcal 27°C K
assuming
-

is =
,

value the above will be

?
for
AH reach
of
 (a) 16.4kcal (b) 18.2 kcal ( c) 15.8kcal (d) 20.0 kcal .

SII Aug
: = 6 - 4 = 2 Du =
17000 Cal

R
?
I
2 cel I
met AM
-
-
=
k =

T 300K DH DU RT
Ang
-
= t
.
=
.

-
'

- DH = 17000 t (2×21-300)
=
47000 t 1200 ) Col
AH -
-
18200 Col = 18.2 kcal Ans
=

Qi Heat
of
reaction
for cog ,
heat
t
Iz 02cg ,
→
cozy , at const .
uol.is

67.71 kcal at 171 The reach at const Pr at 17°C will be

?
g
-
. -
.

(a) -
67.42 Koel ( b) t 68 Keel (c) -
67.71 Keel (d) -

68.0kcal

SOIL : Given :
g. ✓
=
-
67.71 Keel = DU T -
- 17°C or 290k

asked
qp
=

? = AH

R 2 Cal I met I
-

know
Ang
-

K
Liz
wee : = -
=

AH RT
DU
Dng
.
-

.
= t
 '

DH 67710 Col Col

12×2×250
- -
= -
-

.
: AH = -
67710 Gl -

290 Col =
-

68000 Cel

AH = -
688kcal
AI

THERMOCHEMISTRY

Reaction Representation :

Reactants Products I Q Kcal

i
)
-

Co2 94kcal Leno thermic )

Ege Ccs, 02cg t
: t →
,
egg

ii) Reactants - Products ; DH = I Q Kcal

GE Ccs ) t
02cg ,
→
02cg ) ; DH = -

94kcal

Laws
of Thermochemistrylaw
(d) Lavoisier and Laplace :
 At B →
CTD Dn KT (H T P)
; n
-
-

then Ct D → At B
;
AH = -
n KJ Cat same T,
P)

Hess 's Law heat

(2)
of constant summation :

For a
process the heat change will be same
from all

the
different paths involving different no .

of steps .

OR
=

the heat independent of

For amount
given process of is
a

intermediate steps
of
no . .

EF "

→
CO2 Cgg
Ccs ,
02cg ) Usila
-
w :

Ks ¥^
( }
AH
( dHztDH3
0cg ,
=
,

↳ 02cg ) 1202C also DV

,
= DU
z
t
bug

& Using the

following thermochemical reactions :
 Lecture 8
Video Link
https://youtu.be/Ftq1IZcUFuI
 ( i) (
graphite
t
2102cg} 0cg , j DH ,= 110 5 KJ
-
-

Lii )
0cg at 02cg, CO2 Cg ) AH 283.2 KJ
→
;
=
-

, t
,

calculate heat
the
of
reach
for
) (
graphite
t
02cg ,
→ •
aeg ) ; AF ?
Solh :
( is + Cii , = Ciii )
=

Ah dHz
i .

,
t =
dH3
-

110.5 -

2883.2 -
- AH
,
AH
,
= -

393.7 KJ AIS

I Find the heat

charge for the reach :
NHzcggtHUcg,
→
Nltuacs,
the data
using following
:

C) NH , t → NH Ann 8.4kcal
ag Cag )
-

Cg )
.

,
i
.
.
z

Cii ) tell Ha Anz 17 3kcal

@g.g
→ -

*
-

cg , aq = .
.

Cii) Nhzcag ) . t HCl

cog ,.
→
NHuU(agg Anz = -
12-5 Kcal

Civ) Nhu Ucs , t ag .

→ NHUU Cag .
, Aku = t 3.9 kcal .
 (a) -
42.1 Keel ( b) -
34-3 Keel (c ) t 34.3 kcal ( d) t 42 l
-
Kal .

SEI : Rear =
( i) + Cii ) t Ciii ) -

Cb
AH
'

- . = AH t DH
z
t DH - d
Hy
, ,

=
-
8 4
- -
17.3 -
12.5 -
3.9

AH = -

42.2kcal AES

Heat Reactions
Types of of
①
of formation
Enthalpy which ( Dnf ) heat
defined
: It is as the

change occurs when one mole

of a
compound is

elements
formed from its combining in their stable

the
thermodynamic steles under
given
conditions .

at Latin and 25°C :

Element stable state

-_

-11
H2 Cg )
O 02cg )
 Cl Cla Cg )
Br Brr Ce )

I Iz CS )

P Pacs, ( white )

s
secs , ( rhombic )

C C CSI
graphite

EI 2112cg ) t
02cg )
→
21120 ee , ; DH = -
136 kcal .

68kcal Imola
112cg ) t
1202 egg )
→ H2O ; AHF ( Hao ) ⇐
-

Ce ,

element
NOTE : DHI and bat for an in its stable
thermodynamic
state under
specific enperimenbt conditions is
zero
.

}
Latin &
Ege :
Diego ( Brace , ) O at 25°C
-

Anf Crn egg ) to

at Latin 8250C
}
Ahf (graphite ) = o

SHE (diamond ) to
 at Latin B -

Pg Brace , is 80°C

{ 71%9%7??
i. at Iain &
Oo
too "

Q At Latin and which the reactions represent

of
250C
given
enthalpy g fanatic cant )
Ta ) ( t
02cg
→
CO2 egg Dnf ( Coa )
graphite , egg

Yeh ) Nzcg t
3112cg
→

z?zNH3
, )
Cg )
.

€) 112cg ,
t
02cg ,
→
11202 Ce ,
DH f Khao zees )

(d) I Hzcg , t
Iz Brace , → HBR
egg AHF ( HBBr¢g , )

② (
Enthalpy which
of
combustion Ake ) : It is
defined as the
burned
heat

change occurs when I mole

of a
compound is
 completely in
presence of cryogen
to
form stable products after
complete combustion under enperi mental conditions
given
.

EEE
Chu Cg ) t
202cg ,
→

02cg ,
t
2h20 ee , ; An = - 890 KJ

'

890 luol
Dheccnueg ) KJ
-
. =
,
.

which
Q At Latin and 25°C
of
the
following reactions

represents Anc :

ta ) asos
2112cg , t
02cg ,
→ 2h20 Ce )

Ttb ) Calls Cg ) t
SI 02cg ,
→

⑧2cg , t 3h20 ce ,

I) ( Hoo t
602cg ,
→
402cg ) t 4h20 ee , Ahe ( cutlery , )
u
Cg ,
Xd ) C diamond t
02cg ,
→
Coa Atle ( diamond )
g)
Te ) C t 02 Co2 AKCgraphite ) = AH
#
(Co2 )
graphite cg
→
,
g,

NITE :
C) Durden = E
@ F)prod -
E @ Hf) Reactant
 ) Allred = E @ c) Reactants
" - E
@ Hc ) products

¢ Given that standard enthalpies g foemeticnldns )

of Chu , Gnu
and Cz Hq are -
17 -

9 ,
12.5 and - 24.8 kcal Imel respectively .

Then Ate the reach ?

for Chu be
: t
Etty →
Cz Hoo will

Solh :
Chat ca Hu →
↳ Hq ; An =
?
=

I .
AN =
snog ( Cz Hq )
-

( dnf Cena ) t
Atef Cana ) )
Ano =
-
24.8 -

( -

17 -
S t 12.5 )
= - 24 8 . t 17.9 -
12.5

AM = -

19.4 kcal AIS

standard molar hats

of fanatic( notof
Q The ethane ,
co
,
and

water are -21.1 -94 I .

and - 08.3kcal . Then the standard
,

heat combustion ethane ?

molar
of of will be
 (a)
-
162 Keel (b) -

372kcal ( c, -240 Keel (d) -

183.5 Keel .

SOI (2116
cggt -7202cg 202cg 311204 ,
-
: t
,
,

Dhyan = E f) prod -
E @ Ht) Reactants

{2×1-94.13} t {3×(-08-3)} -

{ It C -
21.1 ) ) + {Exo}
Dnyeacn =
-
372kcal
AIs

§ The heat
of combustion
of graphite
and co are -394 and -285

of formation of
The heat
respectively
I will be
mot
?
-

Kismet ' .
co in KJ

(a) t 109 (b)

-

109 (C ) +218 (d) -

218

Sol ? (
Iz 02cg cog, j AHF ( co )
?
→
graphite
t =
,
=

Bureau E @ He )r @ ne )
'

E
'

-
.
=

p
 Lecture 9
Video Link
https://youtu.be/aRlO70nwyQY
 =
C- 394 ) -

C -

285)

All 109 I
'

KJ mel
-

year =
- .

③
Enthalpy ( DH neut ):
of which Neutral isatin
defined
the
It is as
.

heat
change occurs when I
gm equivalent of an acid

neutralised
is
by Igm eg .

of a base .

At 250C and Latin when I acid

of any strong
is
gm eg
.

neutralised
by Lgm of any strong
eg
.
base then the system
releases constant amount heat which
of is :

DH =
-

13.6 Keel leg ( or -13.7 Koel leg )

= -
57 I KJI
eq
.

the
During NaOH
Hclcag , NaCl thou ,
→
reach : t t
cag )
.
. cog ,
the net reach that occurs is
only the combination
of
Ht ion and

OH
-

ion .

Na0H@e.stHyUog.g NayU@a.s Hagee

→ t
,
I
 Nat
@g . ,
tqt Ufag , Natcaqstacag ,
+
H2
-

Htcaq
DH 13.8kcal leg
'

11206
-

) t OH →
; = -

cog , ,
i .
.

g - 13 . ⑥ Kcal I met

In weak acid and weak base to

of
case need
give
we some
,

energy
b- iarise them and i .
net
enthalpy g neutralisatin

will be less weak acid and weak base

of
in care .

DH neut .
=
f- BIG Kcal leg) t
@HicnJw.a t
@ him)w .
B

§ The heat
of
neutral isatin
of
tea
by NaOH is -55-9 Kamel
,
if
heat neutralization luol then the
of by
HCN Naoh 43.8 KJ
of
is -

enthalpy of dissociation
for HCN will be
?
SOI : Annet
'
§
DH neut
5. Ats B

( w
-

)
At S B ) -
= -

=
55.9

-
Kamal

55 S KJ Imel
-
.

t @ Him )w A
-

. .

-
43.8 = -
55 -

S t
@ Him )µcN

(AH ion ) new = t 12.2 Komal

Q In the
following
the
cases at 259 and Latin ,
calculate
enthalpy
change for
i)
rear
g
:

( soul
go.IM
50mL t NaOH
Mason go.IM
of go.IM become
Cii ) 50 ml o -

IM Ha Sou t some

of go.IM NaOH
50 home
Cii )
me O -

IM Chzcoon t

Given @ him )cn coon,

=
(I keel leg ) and @ Mnet )# +s,
=
-
13.6kcal
leg .

Solh :

C) 112504 t NaOH →
Naz u t H2O
=

care . = O IM -

0.1M

Normality = 0.2N o .
IN

Vol .
= 50mL 50mL
 neut 5×10 3cg
to
5
-

i. →
meg =
SF =
m .

eq
.
=
.

@HneutJxne.geg.i
-
: Ah =

fc2.com/ooocdeq)t(5x/oeg )
. An -

-
^

.
An = -

68cal Aus
=

H2SoutCa@h1z-GS0ut2Hz0n.f
Ci )

= 2 2

minds = 5 5

lo
m .
eg = lo

O 01 0.01 → meet → 10cm

eq
0.01
gmeg eq
-
=
= .
.

AH
( 13.6×103
¥) @ Oleg)
'

. .
= t -

An = -

136cal Aus
=
Ciii ) ( ng Coon t NaOH →

5 he → meet Um 4×10-3 eq
eg eq
= =
m .
= .
.

@ Mnet) ( Kolleg)

@Hi:cn7ggcoonpereeeq.n
-

-
13.6 t

÷÷÷÷÷÷÷ :
=

€26 ¥)
x
( 4¥eg ) .

@ Hreacn) =
-

50.4 Cal
AIS
⑥
Enthalpy of Hydrogenation : when I mole
of
an unsaturated

hydrocarbon reacts with required males

of hydrogen to become

saturated og the
enthalpy change involved is known as
 enthalpy g hydrogenation .

Q At Latin the
of following
and 25°C which reactions

represents enthalpy g hydrogenation ?

*
t
Ha -
II
+
(b) H C = C H t
Hz →
Cnz= CUZ
-
-

€'
t
ans -

+
(d) # t Hz →
I

§ The
enthalpy of of cyclohexane combustion ,
cyclohexane and Ha

respectively and 3920 3800 241 KJ / wel Then the

-

are
- -

heat
g hydrogenation of cyclohexane ?
will be

(a) wel l
(C ) 242 met
-

121 KJ KJ
-
-
-

(b)
I
121 nd
I
(d) 242 KF mot
-

t
-

t KJ
Sol ?
=
AH
?
t Hz →
=

Dhruv =
E @ "c) -

E @ Me) prod
Readouts .

{ -

3800 -

241
} -

f -
3920 } KJ

DH
'

. .
= -

404 I * 3920

AN = -
121 KJ Imel

(5)
Enthalpy
Linde
of allotrope
Transition : The

the
heat

element
change which

converted
occurs when

another
of
into
of
an is

allotrope .

E Enthalpy change on combustion

of
2h
guns of graphite
and 36
guns
diamond
of found to KJ
and
respectively og
is be -
200 KJ -
450

then calculate the

enthalpy g transition
from graphite to
diamond .
SEI :

Given :

foe 2ham graphite

combustion

2nd DH
graphite 200 KJ
or → = -

@ Hc) graphite @ HI
'

- -
→ -
look 31 mole

similarly if for 36
gun of
diamond combustion Ah =
- 450 KJ

i.
( Ahc ) diamond
=
-
150 KJI mole

we need
@ 1% , Joe
: (
graphite
→ (
diamond

-
'

- AH
Rear
=
@ he) Reactant -
CA #e) prod

= -

too -

C - 150 )

AH
Reach
= t 50 K Jlmele
HIS
(6)
Enthalpy of Hydration : The heat
change which occurs

salt reacts with

when

one mole
of anhydrous or
partially hydrated
 the required no .

of
water molecules to become
completely hydrated
known
is as
enthalpy of hydration .

the
Q,
which
of given
reactions represent enthalpy of hydration
at Latin and 25°C :

€ Cu 504cg , t
51120µg
→ ↳ SOU -
5h20 Cs )
( it can have wax .

Hii ) soy 21120cg ,

ng ng Sou 0h20 7 water
→

41120g ,
crystallisation
g
.
t .

Cs ,

Xiii ) Na? )
21120 es , 03 10h20
→
Naz coz .
t
81120 Ce ) '

'S )

@gsoq.e 7h20 )

Bond Enthalpies (5)

definedband the particular
heat
It is as required to break a

type of in a

gaseous compound b- either into

atoms radicals
gaseous H
or into
free H
.

Eff u - d H - te - do t
o
H "

KJ Imel
-

l g
DH = n
,
l
.

,
H H
 Lecture 10
Video Link
https://youtu.be/JHAFWCr71ZI
 H
ly
H -

co - -
d .

t .
H ; Anz =
Nz KT Imd .

I l
H
H

ly
E KJ Imel
; Nz
- °
t.tt
-
• c .
AH =
,
l l
H
H

E 0°C t H k Time !
-
Any Nu
a

;
o
✓ . =
o
I
H

{ c- µ =
Nitnrtnztnu KJ Imel Bond ti

energy g
e -

Q Heat evolved in the reach

1kg ,
t
dzcg ,
→ 2ha
egg
is 182 KJ .

Bond and and 242 Kamel

of H I 430
H U
energies
respectively
are
- -

? The H a band will be

energy
-

met I Fb 427 KJ and

I
(d) I
-

245
-

KJ met l
(c ) 154 KT mot
-

KJ 336
-

(a) )
Soi
=
:
dhow =
( Eu ,
t
Ea) -

@ +
En -
a )
-
182 = 430 t 242 ) -
2
EH -

En -
a = 430+242+182 =
427 KJ mot
-

# AH
rear
= I
@ Reactants ) -

E
@products )

Q Calculate the
enthalpy foe
the reach :

CHz= cuz t H2
Cg )
→
CHS -

Chs g,
egg
keel Imel
if Ecu =
99kcal Imel
g E⇐ a
= 147
, EH -
µ
= 104 kcal Imel

and Ee = 83 kcal Imd .

- c

\
SEI ( formed (Energy
Bonds Broken
Energy absorbed) Bands released )
:

- 1471L
I

Cc ) It @
-
- c) 83 =
- C =
-

oak
his :{IT?,
4+99=356 -
n ) =
-554

104 -
 -

Ah -
077
DH
=
= 647 2-
e-

AH
'

Ah 647 30 kcal
= t Anz 677 -
= -
=

pea ,
-

,
.

§ Calculate bond enthalpies of Cis C -

H Cii , c -
c

if Li ) Chace , →
Ccg , t
Uncg ) ; AH,
= 500 Kamel

Cii ) ( Aha 1300 KJ Imel

3118cg ) 34g ,
→

811cg ,
=
t
;
100 KII wel
Ciii ) Chace , →
Chu g, j
Ah
,
= .

SOI :
Ci ) -

Ciii ) Chug , →
Ccg , th
Hg , j @ H
,
-

And -_ bookend .

400 Ut Ec
'

=
n
. .
-

-
'

Ec - µ
=
too KJ Imel bus cis }
( 34g ) kJ1mol
3118cg
DH
811cg , ; 1300
→
) t -

,
-

Bonds broken =
@ +
Eee ) t (Ot Ec -
n ) = AH
 Cdt Ee c) -
t ( 800 ) = 1300

AIS
'

- -

Ee -
c
= +250 KJ Imd

Resonance
Energy
Resonance
energy
is
defined as centra stabilization in a
compound .

[
RE =

@ Ht)enp -

@f) Theo ]
It is
always Eve ) when written in
form of
ash . It is due to

the reason that resonance increases

stability by decreasing
the overall state the molecule
energy of
.

energy difference
Resonance the
energy
is also
defined as

between the stable

resonance
hybrid and most canonical

fam Joey
- :
fd¥m :

y →
f (canonical fans )
 hybrid
t
^ resonance -

then

Energi -

) a
l Higher energy )

-
\ RE

Lo) (Lower energy )

§ Heat dissociation benzene to elements

of of
t
is 5535
-

KJ moi .

The band enthalpies of C -

C
g
C -
-
C and C -
H are 347-3,015-0
calculate the
and 416.2 KJ
respectively .
Then resonance
energy of
benzene :

(a) I. 51 KJ (b) 15-2 KJ ( c) 151 KJ (d) 1511 KJ

Solh :

=
An # 5535k Hmd
X I

④ G)
-

64g ,t Gheg ,

ft
÷¥
RE
Dn
-
-

"

. .. +* . .
=
(3×615) t (3×347.3)+(6×416.2)

Aha =
5384 . I KJ

Using Hess 's Law : dnt DM

,
=
Anz
R .
E t 5535=5384 I .

I .
Rio E = 5384 . I -5535

R E .
Fr -

151 KJ
Q Calculate
.
the heat released on
complete combusting
data
Mgm of Ccgsapwie )
by using the
given
.

DH ( ( ) N
E②=o Nz Ec=o =

Nz
graphite
=
sublimation =
, g g

and Atlrescnance ( CO2 ) =

Ny

Are ?
( with Resonance )
Ccgraphite
"
Sol CO2
t
02cg
" -

=
)
Cs )
, egg

AMEN ,

(
I ↳ Nz
-
-
Nz

{ Aku = Ny

Cg )
#
20cg ) o=C= O
Cg ) ( without
Resonance)
Anz =
-

223

law
'

-
.

Using Hess 's : AH = AH

,
t AH
, tasty +
Any
DM =
4 ,
t nz
-

2n
, tna ) Cfd Inde
graphite)
= .

Jd Linde
graphite = An = 2 (n , tnz -

Znztnu) AIS
 2nd Law
of Thermodynamics
2nd law helps us to determine the direction in which
energy
be helps predict whether
can
transferred .
It us to a
given process
or chemical reaction can occur
spontaneously . It also helps us to knew

the conditions chemical

of
reach
egm a .

"

Statement to tract heat

It impossible cyclic
: to en
is use a
process

from a reservoir and to convert it into work without

transferring heat
from hotter
certain amount
part
of
a a

the
' '
at
to colder
a
part of
the
body same time .

OR
=

"
also stated the the
It is as
entropy of universe is
constantly
'9

increasing .

mathematically : DS universe = AS
syst
AS
sun
70
Entropy ( s)
Entropy the
of randomness
: is measure disorder
or .

enter sine
It is a state
funen and an
property
.

mathematically
dj fd9
,
ds = or Ds =

( Ds )
Entropy change and
spontaneity :

For a
spontaneous process in isolated
an
system ,
the
change
in
entropy is tune .

Egf Mixing kept isolated

of
in an container
gases
.
.

÷:÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷:÷: DS > O
=

If the system is not isolated then the

entropy change in both

the and the taken into account

surrounding
to be
system are
and
( system make Therefore
t
surrounding ) an isolated
system .

d-
Szoke =
Asap t Assur > 0

NOTE :
(i ) For a reversible at egm AS -

o
process
-

Lii ) For an irreversible

process
( spontaneous )
fed an isolated

As
system
>o .

which
§ In
of
the
following reach

AS
AS will be tire
?
(a) H2Qe , →
1120cg ,
LO

(b) 302cg 203cg ) Dng Lo Ds co

'
→
,
.
.

Ic ) Hzoce ,
→
H2O Cg ) DS > o @ ng >o )
(d) Nz 3112cg 2NH3cg ) Anglo
→
t
Cg ) )

Q the
Mgcozcs Mgocs cozy will be ?
for
→
DS reach : t
,
, , ,

Zero Ib) (d) None these

of
tire
(a) (c) - ve .
 Lecture 11
Video Link
https://youtu.be/weet2gmA3Zg
 Calculation
of change Entropy
in :

①
Entropy change in a reversible
process
:

Considering an isothermal reversible

process ,
in this
process
heat
system absorbs from
"

the
ofthe
amount
"

g surroundings
temperature Therefore
" "

at T . increase in
entropy of the
system can be written as :

Dssgs =
TI
T

On other hand loose the

the
surrounding will same amount
of
heat decrease the
entropy of surrounding
'

.
. in cam, be written

as :

Assur = -

q
t

change entropy for the

i Total will be :
.

in process
D. Sydal =
Dssygt Assume =

toy I
-

= O
 Now
calculating As
for system
:

Dssgs tq=

-
'

of
=
Tdssyg dq = Tds
-

①
[from ist Law : du
Gtw q
= DU w ]
-

day .
. du -
dw -

Using ① and ②

n.fi:1: I:S ( ta ingen :: ]

- :
"

( )
faidedgm .

nyId¥=ds
n a +

Integrating both sides

In Cudi tfnrdy =
fds
 (¥)
tu
i
ng en t n r
(÷) = AS -

③
also
for an ideal
gas
: i

1¥ =

R÷z
"
Ii ¥ -
-
-

¥
-

Using ③ and ④

u cuh (¥ ) t n R In .

¥)
= as

nev en
¥) t ar en
(¥ ) t n R k
(¥ ) = AS

nccu tr ) In
(¥ ) tnr k
ftp. ) -
-
as

n
Cp ln (¥ ) t n R k
(Apg ) = as
 5 moles ideal
Q
of Jam g
8dm '
gas empanels reversibly
an avoir

to 80 dm ? at a
temp of 27°C The
-
.

change in entropy
the ?
of (a) system will be

41 57 Jk I
(b) I
95 73
I
(d) 41.573kt
-

95.73 (C)
-

Jk
-
.
- .
Jk -

SOI : n' - 5
Tz = T
,
= 300K V2 = 80dm ? = 80L

Vz = 8 dm ? =
8L

tu
as nu
(¥ ) tnr en
(
.

: :

( 8oz)
'

l
5×25
. . As = O t
x -

51-235-+2.303 leg Clo)

125×32--303
i .
DS = = = 95-95 Jk I
-

Ans
=

§ If one mole
ofuntil an ideal
gas (Cpm -
-

SIR ) is
empaneled isothermally
at its volume
Zook is tripled .
then
change in
 the ?
entropy of gas
will be

(a) Zero Cbs

infinity (c)
SIR
l - 3 Id) R In 3

②
Entropy
Consider
change in

at
irreversible process :

temp (7) its

a
system a
higher . &
surrounding
lower temp th ) heat
at a . .
If (
q ) amount
of goes from
system surrounding spontaneously
to then :

Asap I
and

t÷
Assur
-

= =

Astolat (¥ ¥)
:

÷ ÷ 9
-

=
-

t = -

9
( Tietz) f T, > Tz LT Tz) > }
'

= : r
: -

o
.

i D
.

Stone > O
 transition
Entropy change during phase :

①
Entropy of fusion : the
entropy change when Inde
of a

its
solid

substance
changes from solid state to liquid stab at
melting
point known its
is as
entropy of fusion .

DS
9rv
. .

.
=

( at caret
and
for fusion og
grew
=
DH
fusion
.

temp .
&
pr )
.

and
temp = 1-
fusion

A- DH
Sfu
'

. .

,
=
fusion
-

T
fusion

the
fusion of
water
Q
=
Find
entropy of if standard
enthalpy of
fusion for
"
water 6 is KJ per mole at 273K and I bar pr .

Gol : -

.
.

As =
DI
T T
 Lecture 12
Video Link
https://youtu.be/kkHlSHiCQ2A
 I
60003 trot
'
A 21 97 JK mot
- -

I
Sfo =
. .
-

, in
¥31
In 22 Jk
- I
met
-

②
Entropy of vapour
isatin : Linde liquid →
vapour

DS
rap
=
dtlap
Trap

③ Inde
Entropy of sublimation solid
vapour
→
:

AHH
Dss Ub =

-
sub

T
sub

Gibbs Free (a ) &

Energy Gibb 's Free
Energy change CDG)
 have that
We seen
fee a
system it is the total
entropy
( Astolat )
change which decides spontaneity of a
process
. Most

the chemical either take closed

of
reactions
place in a or
open

system and
therefore there are
changes in both
enthalpy and

the
entropy gNeither system .

a decrease in
enthalpy nor an increase in

alone determine the

entropy can direction
foe spontaneous change
in a
system .

this
Hence ,
for purpose we
define a new
thermodynamic Lunch :

Gibb 's / Gibb 's (G)

free energy funen
work which
ee
Gibbs
The
energy of
a
system is
defined as
,
The
useful
(a) mathematically
be
from
' '
obtained the
can
system .
is
given
as :

G -

-
H -

TS

where : H :
Enthalpy T: Absolute temp .
S: Absolute
entropy
of the
nys .

Y the
sys .

of
the
ng
.
G is an enknsive
property and a state
Lunch . The
change in

Gibb 's
free energy for the
system can be written as :

da = DH -
d CTS )

dG -
- DH -

Tds -
Sd T -

foe a chemical reach

AT = O
or a
thermodynamic process
at a
given temp ETD

i
from ① da = d
Hap Tdssyg
-

sup
.

A
Gap =

dhsys T
Dssys
-

For a
spontaneous process : A
Stoke > O

Ah
sup
Lo { i

-
'

D
Gsp =
-

TDs
total }

For
any chemical process
: Dh =
(G)prod .
-

(G)Reactants
Q If Dn > then the
,
o and AS > O
g
reach
proceeds spontaneously
when :

€3 AGCO
for
AHL
(a) An > o Tds spontaneous
!
'

④ D. no (d) An > TDS - -

Ah -
toss < o

=3 An L Tds

at
§ For a reach

'
25°C
enthalpy .

change Cdn ) and

entropy change Cds)

respectively the
'
-11.7 No J mot
'
and 105 J mot K I
Then
-

are .

rear is :

Ia spontaneous
, DH = -11.7×103

(b) Non spontaneous

-
DS = 105 -

T -
(C) At egm .
= 298

(d) Data
insufficient da
II tss
-
-
-

- ve
try
- ve

Da Lo
spontaneous
.

=
-
ve .
.
 AH DS
magnitude da

C- ve
) f- ) Eve ) spontaneous
any
ve

f- ve) C- ve ) fire ) Non spontaneous

any
-

f- ve )
f- ve
) (Dnf Hss ) C- ve) Spontaneous
f- ve ) f-
ve
) Mnf Hast Eve ) Non -

spontaneous
fire ) ft ve ) 1dm c Hast f- ve ) Spontaneous
fire) fire ) 1AM I > kiss ) fue) Non -

spontaneous .

NOIE :( is At egm conditions da = o

Cii ) ( AG = -

Wuyue )
ie
Lega the Gibb 's
free energy change ,

greater is the amount

of
work that can be obtained

the process
fear .

is For
calculating efficiency of fuel cell :
y laden )
-

a -
§ For the reach :
Ag > Ocs , → 2
Ages ,
+
I 02cg , the value
of
at
the temp
t
AH I and met Then
-

30.56 KJ mot As 66 I
-

Jk
-
= = .
.

which the
flee change for the reach will be o

is
energy zero
.

(a) 493k (b) 463K 43 413K (d) 373k .

SOI DM Imd 7
'
-
I
30560 J mot DS 663 K T=
-
: = =

DA -
-
O

'

. .
DH -
TAS =
O

463
Aft
T = 30560 = K
=
-

-66

§ At 0°C ice and water are in

egm and An = G les moi
-
'

for the

process : H2O Css = H2O ice )

The value
of
DS and da
for the above egm reach will be
?
Seth : Da -
-
o

Ah
Atf
'

Tds AS
6203g
' "
22 Tmd K
- -
=
⇐=
- -
.

=
 Some other relations
Useful for da

Da is a RT In Q
°
i) = t

ii ) At egm da -

-
co .
.

.
O = doit RT link

Q RT
and =

Keg Dao = -

lnkeg

Ciii ) Gibbs Helmholtz Gen : da = Vdp -

SDT

( v) AG = - n F Eau n → no -

of moles

F- →
Faraday 's const f- 96500C )
Ecole F- MF cell
of
→
.
Absolute Entropic ② Law
of Thermodynamics
Third

"

statement At absolute the

perfectly crystalline
entropy of
:
zero a

taken
substance or a
pure crystalline substance is as

99

Zero
.

solid liquid approaches

"
It is also stated as :
Entropy of a or
zero
at absolute temp "

zero
.

mathematically :
limo
5=0

Limitations :

( amorphous ) at
D
Glassy solids even
zero
Kelvin have en
tropics >o .

2.) Crystals
of
co
,
No
, Hao etc do not have
perfect order at
zero
Kelvin .

have
3.) Solids having mixtures
of isotopes do not
zero entropy at o Kelvin
.
Calculating entropy of a solid at LT ) Kelvin
DS St so
. .

= -
.

So DS
i .

Sy = t

and
foe perfectly crystalline substance so = O

Sy fds
fd9÷ev
'

-
-
= AS = =

: '

St =

fncpd÷ qq.li?akeptatacenst.pr-)
i .

St =
ncp lute ) ( if Cp is independent of temp )
.
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