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PHYSICAL

CHEMISTRY I
I C- DR. RANJAN DEY
Calculation of First Law
Quantities and Second Law
An infinitesimal change in conditions can reverse the process to
restore both system and surroundings to their initial states.
A reversible process is obviously an idealization
Line Integrals
The integral given in earlier expression is
A rev process is one in which system is
infinitesimally close to eqb.
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The integral given in earlier expression is
called line integral
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Exact and Inexact Differentials
A state function is a property that depends solely on the state of the
system. It does not depend on how the system was brought to that
state.
When a system is brought from an initial to a final state, the
change in a state function is independent of the path followed.
An infinitesimal change of a state function is an exact differential.
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Internal energy : state function
: exact differential
, independent of the path
f
f i
i
U
dU
dU U U U = =

An infinitesimal change of a state function is an exact differential.


Work and heat are not state functions and do not correspond to
exact differentials.
Of the three thermodynamic variables, only two are independent. It is
convenient to choose V and T as the independent variables for U.
The First Law
U q w = +
The sum of the heat q transferred to a system and the
work w performed on it equal the change U in the
systems internal energy.
According to First law, the total energy for any process,
FIRST LAW OF THERMODYNAMICS
E = Closed system
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U q w = +
Postulate: The internal energy is a state function of the
system.
Work and heat are not state functions and do not
correspond to exact differentials.
dU dq PdV

=
E =
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From First law: U= q + w
( )
f
i
V
V
w PV dV =

U
2
U
1
= q +w
U
2
U
1
= q
P
P(V
2
V
1
)
q
P
= U
2
+PV
2
- (U
1
+ PV
1
)= H
2
H
1
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P 2 2 1 1 2 1
q
P
= H constant P, closed system, P-V work only
H = U + P V, constant P
U = q
V
, closed system, P-V work only, V constant
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Heat Capacities
The heat capacity of a closed system for an
infinitesimal process is defined as
C = dq/dT, dq and dT are heat flowing into the
system and temp change of the process.
For constant pressure process, we get C :
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For constant pressure process, we get C
P
:
C
P
= dq
P
/dT = (H/ T)
P
For constant volume (isochoric) process:
C
V
= dq
V
/dT = (U/ T)
V
C
P,m =
C
P
/n ; C
V,m =
C
V
/n (molar heat cap.) &
c
P
= C
P
/m ; c
V
= C
V
/m ( specific heat cap.)
In Cyclic process any change in state function is zero.
H = U = P = T = V = 0
In isothermal process, U is constant (Can be achieve b!
enclosin" s!stem in a thermall! con#ctin" $alls an place
it in constant T bath%
In adiabatic process, dq=0 and q=0(Can be achieved
Calculation of First Law
Quantities
BITS Pilani, K K Birla Goa Campus
In adiabatic process, dq=0 and q=0(Can be achieved
by surrounding system with adiabatic walls)
In Constant volume process, work is zero , provided system is capable of
doing P-V work only (Can be achieved by enclosing system in rigid
walls
In constant Pressure process, = q
P
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Reversible Phase change with constant T&P
Phase change or phase transition is a process
In which a new phase appears in a system without chemical Rx.
Eg., melting of ice to liquid water, freezing of ice from aq solution.
W = -P.dV; = q
P
! U = q + w.
Constant Pressure heating with no phase change
w = w
rev
= -P.dV ; = q
P
; U = q
P
+ w
Constant "olume heating with no phase change
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Constant "olume heating with no phase change
w=0, U = q + w = q
V
; = # $ "P
Per%ect &as change o% state
d# = C
"
d' , d = C
P
d'! w = ()
1
2
Pd" = ()
1
2
(*+')d"
*eversible isothermal process in a per%ect gas
= 0 and # = 0! w = (n*' ln("
,
+"
-
)! q= (w.
*eversible adiabatic process in a per%ect gas.
/=0, w = #! P
-
"
-
0
= P
,
"
,
0
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Adiabatic expansion of a perfect gas into vacuum
q=0, w=0, = # $ (P") = # $ n* ' = 0
'he 1I unit %or q, w, # and are 2oules.
MechanicalWork
ReversibleProcesses
ReversibleIsothermalExpansion/CompressionofIdealGas
ExactandInexactDifferentials
TheFirstLaw
WorkandHeatalongReversibleIsothermalExpansion
foranIdealGas,whereU=U(T)
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SECOND LAW
q
C
is ve for the heat engine since +ve heat
flows out of the system to the cold body.
Efficiency, e, of a heat engine is the fraction
of the energy input that appears as useful
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of the energy input that appears as useful
energy output, that is, appears as work.
e = work output per cycle = -w = |w |
energy input per cycle q
H
q
H
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e = 1 + q
C
/ q
H
,
efficiency is less than one as q
C
is ve, q
H
is +ve.
CARNOTS PRINCIPLE
No heat engine can be more efficient than a reversible heat No heat engine can be more efficient than a reversible heat No heat engine can be more efficient than a reversible heat No heat engine can be more efficient than a reversible heat
From I
st
law: U =0= q +w
= q
H
+q
C
+w; -w = q
H
+q
C
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No heat engine can be more efficient than a reversible heat No heat engine can be more efficient than a reversible heat No heat engine can be more efficient than a reversible heat No heat engine can be more efficient than a reversible heat
engine when both engines work between the same pair engine when both engines work between the same pair engine when both engines work between the same pair engine when both engines work between the same pair
of reversible heat engines working between the same of reversible heat engines working between the same of reversible heat engines working between the same of reversible heat engines working between the same
pair of temperatures pair of temperatures pair of temperatures pair of temperatures
H HH H
and and and and
C CC C
.
The ma&im#m amo#nt o'
$or( 'rom a "iven s#ppl!
o' heat is obtaine $ith
reversible en"ine
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For any closed system undergoing a Carnot cycle, integral of
dq
rev
/T around the cycle is zero.
If it is irreversible, it cannot be related to the Carnot cycle and
the above condition need not hold.
Since integral of any rev cycle is zero, the value of line integral
ENTROPY
BITS Pilani, K K Birla Goa Campus
Since integral of any rev cycle is zero, the value of line integral

1
2
dq
rev
/T is independent of path between states 1 and 2 and
depends only upon the initial and final states. Hence dq
rev
/T is
the differential of a state function and is defined as
entropy, S.
dS dq
rev
/T closed system, reversible process.
Entropy change in going from state 1 to state 2 is
S = S
2
S
1
=
1
2
dq
rev
/T
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Commonly used units of entropy are J/K or cal/K.
Corresponding units of S
m
are J/(mol K)
C34C#43'I56 57 86'*5P9 C36&81
For cyclic process: S = 0
Entropy is an extensive state
fn
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For cyclic process: S = 0
For reversible adiabatic process: S = 0 as dq
rev
= 0
Reversible phase change at constant T and P : S = q
rev
/T
q
rev
is latent heat of transition at constant T and P. Thus
q
rev
= q
P
= H S = H/T rev phase change at const T&P
Reversible isothermal process : S = q
rev
/T
Constant Pressure heating : S =
T1
T2
C
P
dT/T
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1. Rev warming supercooled liquid to 0C and 1 atm
2. Reversibly freezing it at 0C and 1 atm
3. Reversibly cooling the ice to -10C and 1 atm
Mixing of different perfect gases at constant P&T
S = n Rln(V/V ) + n R ln(V/V ) for irr mixing
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S = n
a
Rln(V/V
a
) + n
b
R ln(V/V
b
) for irr mixing

mix
S = - n
a
Rln(x
a
) - n
b
R ln(x
b
)
S
univ
= S
sys
+ s
surr
s
univ
=0 for reversible process
S
univ
= S
sys
+ s
univ
remains unchanged in a
reversible process
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