&

NOTEEPARED
BY

AFA S
MUST
m mIR

MUSTAF.S. B
#
 WHAT IS THERMODYNAMICS I

Thermodynamics
is a branch of
physical chemistry
that deals with energy changes,
and
transformation

Terms related to Thermodynamic

& universe under Thermodynamic
A part of
em. is called as
system
investigation

universe than
A part of
other
system
Surrounding:
~
is called as
surrounding

TYPES 0 F - YSTEM

as on statem: system which

exchange
both matter and energy with the surrounding.

system:
6) C
A
system which
exchange
but not matter with sounding.
energy
which
heighter
ard system:
#
A system
C)
with
exchange matter nor
energy sounding
 PROPERTIES OF SYSTEM

Extensive
# Property: A
property of system which
↓ the
epends on amount of matter present in a

System eg:.
mass, volume

B) Intensive Property: A property of a

system which is

independent on amount of matter.

density. Pressure, Temperature

eg:
TYPES OF FUNCTION

#)STATE FUNCTION: Function which are

dependent on

initial and final state.

Pressure, volume
eg:

of which
3) ath Fraction: The property system
are dependent on path
etc
eg: Heat; work

PROCESS AND ITS TYPES

ermal process. in which

#

AS Process

remains constant (Dr =0)

Temperature
Process in which
B) Ebaris less.
constant (DP=0
remains
pressure
Process in which
poless:
horic
=

C)
remains constant (by = 0)
volume
 abatic cocess:
# Process in which
DS
heat (q 0)
=

of
no
exchange
in which
asible
ES # coless: A process
cause the
infinitesimal change may
any
process to occur reversible

↑
eatures Reversible
of Process

force is infinitesimal greate

1) Driving
Force
then opposing
2S Process can be reversed by ame

small
change
in infinite
Process
3)
proceeds slowly and

number of steps

4) If attains mechanical equilibrium.

lance of Hear and Work

1w Fxd =

work is the product of force

and displacement
Pressure
* - volve work

xPX FxX....(P )
=

Xd
=
Fxd
:Force & displacement
=>

PX = work
-

work of expansion work of Compression

the is done the

work is done
by work
by
system on the scrown
surrounding
system.
on the

ding
always. This always
work is
work is
This
C positive)
Inegative
 5) GN AND CONVENTION OF N and O
1

done
+x = work
by surrounding on
system

-
N =
work done by system on surroundin
a
+
=
Hear is absorbed

: Hear is evolved

↑one: W and C are path Function.

Expression For Pessie volume (PY)

&
We know that; #or: while writing
F = -

Pex XA-0 derivation please

with
AlsO; write along
w Fxd- @
=
Proper Statemal-
①
substituting &
in
a
Use this as
w =
-

Pxx xAxd weperence

xY = Axd -

B
i. U = -
PexXY
Free expansion: opposing Force
Expansion against zero

is called as free expansion.

one;
↑ zero
opposing force is Pento
. 00 = -
Pen DX
.

w=0 (No work done)

--
-

Important conversions

Concept of Maximum work.

the
The amount of work performed by system
is
governed by opposing force (Per).
a

larger opposing force,

the done
more is the work
by
the
system to overcome it.

when the
opposing force becomes greate
than the
driving force; the process gets
reversed
work (ws would be maximum when p
The
i
s smallest.
 Expression for maximum work

each external
During step
Pressure Paris made

infinitesimally smaller than

the pressure of the gas.
when the volume of a
gas
increase
by an infinitesimal
amount dy in
single
a
step
than the
quantity of work done
du =-Peody - O
As the
expansion is reversible: P is greater by a

very small
quantity dp; Thus
p -
Pex dP =

Pex
=

= P- dp -

both 1 and @
combining
dw =

dp)dx
-

p.dx
(p- +
dp.dy = -

#
eglecting (dp.dy) which is very small
We
get;
dw = -
p.dx -

Integratingboth
sides are

Y( Y2
Hence Wmax
=

S,, p.dy
-

using ideal
gas equation
PX hRT =

-2
wman
x. UR+d
= -
 Wmax
nR+("IT
=-
is constant)
wmax nRT
(x)
=-
In

nRT(OnYz
=

1nX,
-

=-
nRT In Y2
-

X
↑

*2
wmax=- 2.303nRT 10g. #

At Constant temperature P.x, =

Peve
er

H =

E
Replacing aboveequ by
o
to
in

wmax = -

2.303nR+ 109. Ez

Internal Energy
The energy of a system is made
internal

up of kinetic
and
potential energies of an
individual particles of the system.

0 Uz V,
=
-

where U2 and 0, are internal energies of

final and initial scares.

Note: U is a scale function

 First Law of Thermodynamics
to this law; the toral energy
According
constant
of the system and surrounding remains

when the system changes from initial state

to Final state.

u = G + W

DV increase in internal energy

where =

of the system

First law of Thermodynamics For various process

->sothermal Process (DV 0S =

Xu 0 + w =

0 + w
0 =

c
:B wa.w
= -

-
=

aric Poess.(xP 0S
=

xu c = + w
u c+ C
* =
-
PenDNS
xu =
0 + 0
: -
xu 0
=

Adiabatic Process · (C 0)
=

Xu 0 =

+ w

Xu 0 + w
=

XU = w

Foric Press. (XP 0S =

Xu 0 = + w

x v =
G -
PenDY
↓
. 0 = x U +PenDY
 ENTHALPY CHANGE
the
enthalpy of a
system is sum
of
and
internal energy of system
a the
energy
equivalent to pressure-volume work.

H u +
=
PY

-teoi
1
t H,
=
He
-

=
(uc + PzXz) -

(u, + p,x,) +Pbx

Xu + PDX/
=
(uz v) cPcXz-
+
-

P,y,) x H =

=
x + b(PY) ·
. H 0 =

For Constant Pressure;

↑1 P2 =
= P

&a H Xu + PXY
x =

elationship
R between DH and DU

At Constant Pressure;
* H DU + =
PSY
usually small
a) For solid and liquid; DX is
very
i
neglecting Dx; <H= DU

b) For reaction involving gases;

H Nu
* =
+ PXY

1u +
=
P(Xe -

x1)
=
XU+PYz-PY,
~ here X, and Ye are volume reactant and
of productof
gas phase reachou

ideal
According to gas equation;
PX xRT =
· . DH = xU + (HeRT-n(RT)
↑Y, 4,RT=

H
* = DV + R T(X U)
↑ Xz ncRT =

:
DH= NU + AURT
 WORK DONE IN CHEMICAL REACTION

at constant temperature
work done by
a
system
and pressure
is
given by
=- Pen DY

CAssuming Pen = P
.w -
=
PAX

to ideal gas equation;

according
PY = nRT
↑x, n,
=
RT i PVe =McRT

p(Xc x1) - =
-

(PXz- PX
S w -

(xcRT x,RT)
=
-
-

=
-
(Hz )RT -

-
w =
-
AURT

e; IF Vesni; Dn=
positive;
0 =
negative
-

*Fn.>Uc; Ane negative; n= positive

12; Dn 0,w 0
fu,
I
= = =
 Types &F Enth alpies
AEnthalpy of Fusion: Enthalpy change that accompanies

Imoke of solid
to liquid at constance

during conversion of
and pressure.
Temperature

vaporisation that accompany

Enthalpy
B) of enthalpy change
into
mole of liquid vapors
during conversion of one

at Constant temperance
and pressure
&

during
Enthalpy
2) of vaporisation: Enthalpy change accompanies
-

solid without converting

conversion
of one mole of directly into
gas
into
liquid at constant temperate and pressure
8)Enthalpy oF Fonization enthalpy change
removal from
accompanying the of an electron

one mole of gaseous arom

enthalpy is enthalpy
enthalpy
=>
of gain electron: Electron
gain element
atom of an
that accompany when the mole of gas phase
change
accepts electron to form anion.
gaseous

of solution enthalpy change in a

Enthalpy
#

substance is dissolve
when one mole of a
process
in
specified amount ofsolvent.

THERMOCHEMISTRY
Reaction
Enthalpy of a chemical

Consider a chemical Reaction;

aA 6B
+

ccdD +

xH (+c+ d(x)
=
-

(a+
A +
bHB)
-a

H 2 H
* =

product
-

2Ireactant

Enthalpy of chemical reaction is the difference

between the that of
sum of enthalpies of product and
reactant with each substance in definite physical
srare
being represented by co-efficients in a

↓ alanced chemical equation.

 #
XOTHERMIC AND ENDO THERMIC REACTIONS

Endothermic Reaction.
ive =

momt

Exothermic Reaction
-gative
:

Standard Enthalpy of Formation

standard of Formation of a
The enthalpy
that
compound
is the
enthalpy change
reaction in which one mole of a

accompanies a
its element
in its standard state is formed from
pure compound
standard states.
in their

-
 standard enthalpy of a reaction.

Consider a reaction;

aA+ 6B -> c2 + dD
is
standard enthalpy of reaction
given by
xv (xHi
=
+
d() -

(a+in +
B)
6+

ED
=

product
- EDti reactant

Standard Enthalpy of Combustion

The standard enthalpy of combustion of a

& ubstance is the standard enthalpy change

reaction in which one mole of a
accompanying
a

Substance is completly occidised.

OND
B ENTHALPU

The enthalpy change required to break

band in one more of

particular covalent gaseous
produce arom radicals
molecules to
gaseous or

↑
s called bond enthalpy.
 HESS LAW OF CONSTANT HEAT

for to sum
enthalpy change reaction of
is
equal
T
a
he
individual reaction.
enthalpy changes
in the
of steps

Energy and S
ponrancing
is criteria decides
Energy
not
only which

of the process.
the spontaneity
TROPY

disorder or measure of randomness is measured

by entropy
The
the disorder of the system larger
's: Greater
denoted by
entropy
i

ts

S econd law of Thermodynamics

The law states that "total entopy

and surrounding increases in a
of a
syspe
spontaneous process
i. B Storal > O
 GIBBS ENERGY
and
Relation between storal
DEFINED
ENERGY
99
IS As
9 IBBS

a
* =
DH -
TAS

Assun s
-
=

*
a =
change
in Gibbs Energy
-
Isroval = 9S
*
H Enthalpy change
=

P
T:
Temperature Thus, TS
Stotal" SH-TDS -

xS: Entropy Change AlsO;

xn -
TAs 9a =
-
Q
From O $@
1a =
-

T AS
total

*TE 8

Temperate
at equilibrium
TDS
A4 DH
-

DG 0
equilibrium
=
;
At
T $S
80 DH =

=
i. T
 FUNCTION AND EQUILIBRIUM CONSTANT
GIBBS

&4 = DY" + RT In U.
is called as reaction Quotient
where a

Consider a reaction:

aA + 6B -> c + dD

InO
A4 x4 + 1 +

Incin
=

s4 +
->
R+

At equilibrium DU = 0 ;

0 = x4 +RT In K
DC=- 2.3031+10g..K
.

or
: xc.-RTink,
AND
T
-

ci=-2.303RT109.Kp
x (For Gas phase Reaction)

↑
HANK You
MUSTAFA
#
SIR