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THE COMBINATION OF FIRST AND SECOND LAW OF

THERMODYNAMIC
A. A Combination of First And Second Law of Thermodynamics
Analytic formulation of the thermodynamics law is:
W d q d dU
......................................................................(1)
and analytic formulation of Thermodynamics Law II is:
dS T q d
rev

..........................................................................(2)
If both of them first and second law combined then obtained equations as follows.
W d q d dU
W d dS T dU
...................................................................(3)
It is known that
dV p W d
so:
W d dS T dU
dV p dS T dU
.................................................................(4)
By using equations (4), then the relationships of other thermodynamic can be
determined by taking a pair of coordinates of thermodynamics as a free variable. It
is well known that the U and S is a function of the system state can be expressed by
two coordinates thermodynamic anywhere. For example the U and S are expressed as
a function of T and V then mathematically can be written:
) , ( V T f U

and
) , ( V T f S
, then the total differential is:
dV
V
U
dT
T
U
dU
T V

,
_

+
,
_

................................................(5)
dV
V
S
dT
T
S
dS
T V

,
_

+
,
_

..................................................(6)
If the equations (5) substitute into equations the combination of law I and II
of thermodynamics (equation (4)) then retrieved:
pdV TdS dU
pdV dU TdS +
pdV dV
V
U
dT
T
U
TdS
T V
+
1
]
1

,
_

+
,
_

Combination of First And Second Law of Thermodynamic Page 1


By Tenth Group
dV
V
U
p dT
T
U
TdS
T V
1
]
1

,
_

+ +
,
_

dV
V
U
p
T
dT
T
U
T
dS
T V
1
]
1

,
_

+ +
,
_

1 1
So,
V V
T
U
T T
S

,
_


,
_

1
...............................................................(7)
1
]
1

,
_

+
,
_

T T
V
U
p
T V
S 1
.......................................................(8)
So that equation (7) and (8) can be expressed with quantities measured, can be done
by applying a mathematical concept i.e. If z is a function of x and y. then:

,
_

,
_

x
z
y y
Z
x

or
x y
z
y x
z

2 2
so:
V
T
T
V
V
S
T T
S
V
1
]
1

,
_

1
]
1

,
_

..............................................(9)
By substituting equation (7) and (8) into equations (9) then retrieved the equation as
follows:
V
T
T
V
V
U
p
T T T
U
T V

;

'

1
]
1

,
_

1
]
1

,
_

1 1
1
]
1

,
_

+
1
]
1

,
_

+
,
_

T V
V
U
p
T V T
U
T
p
T T V
U
T
2
2 2
1 1 1
V T
T
p
T V
U
p
T

,
_

1
]
1

,
_

+
1 1
2
V T
T
p
T
V
U
p
,
_


,
_

+
.........................................................(10)
p
T
p
T
V
U
V T

,
_


,
_

Combination of First And Second Law of Thermodynamic Page 2


By Tenth Group
Using the relations:
1

,
_

,
_

,
_

V
p T
p
T
T
V
V
p
or
p T
V
T
V
V
p p
T

,
_

,
_

,
_

1
or
p T V
T
V
V
p
T
p

,
_

,
_


,
_

then the retrieved:


p
T
V
V
p
T
V
U
p T T

,
_

,
_


,
_

p
p
V
T
V
T
V
U
T
p
T

,
_

,
_


,
_

where
V
T
V
p

,
_

and
V
p
V
T

,
_

, then the retrieved:


p
T
V
U
T

,
_

.................................................................(11)
If this equation applied to the ideal gas system, where
T
1


and
p
1

then the
retrieved:
p
p
T
T
V
U
T

,
_

1
1
0
,
_

T
V
U
So, the energy in an ideal gas is independent of the system volume. Previously it was
known that the:
p T
V p
T
V
p
V
U
C C
,
_

1
]
1

+
,
_


. By substituting it with the equation
(10) in the equation is then derived the equation:
p T
V p
T
V
p
V
U
C C
,
_

1
]
1

+
,
_


p V
V p
T
V
T
p
T C C
,
_

,
_


Combination of First And Second Law of Thermodynamic Page 3
By Tenth Group
Using the relations
1

,
_

,
_

,
_

V
p T
p
T
T
V
V
p
or
p T
V
T
V
V
p p
T

,
_

,
_

,
_

1
or
p T V
T
V
V
p
T
p

,
_

,
_


,
_

then the retrieved:


p p T
V p
T
V
T
V
V
p
T C C
,
_

,
_

,
_


T
p p
V p
V
p
T
V
T
V
T C C

,
_

,
_

,
_


Where
V
T
V
p

,
_

and
V
p
V
T

,
_

, then obtained:
( )( )
( ) V
V V
T C C
V p

V T
C C
V p
2
..............................................................(12)
By using the equation (12), the difference between the Cp and C
V
can be
calculated for each solution are already known and his only . Price T, V, and is
positive, but the price could be positive, is negative or zero For water at
atmospheric pressure and temperatures of 40 c, = 0 and between 0oC to 40 c
value is negative (anomalous properties of water). Therefore always positive or zero

2
and Cp > C
V
.
B. The Differential Partial Entropy
As known that entropy is a function of the State of the system, so it can be
expressed as a function of two variables to another.
1. S as a function of volume (V) and temperature (T)
In mathematically: S = f (T, V), the total differential is:
dV
V
S
dT
T
S
dS
T V

,
_

+
,
_

..........................................(13)
Combination of First And Second Law of Thermodynamic Page 4
By Tenth Group
Known that:
V V
T
U
T T
S

,
_


,
_

1

and

V
V
C
T
U

,
_

so,

V
T
C
T
C
T
S
p
V
V
2

,
_

............................................(14)
By substitution the equation (11) to the equation (8), so can obtained:
1
]
1

,
_

+
,
_

T T
V
U
p
T V
S 1


,
_

T
V
S
....................................................................(15)
By the return differentiated of partial differential S in the equations (14) and
(15), can get the equation:
T
V
V
T
T
S
V V
S
T
1
]
1

,
_

1
]
1

,
_

T
V
V
T
C
V T
1
]
1

,
_

1
]
1

,
_

V T
V
T
T
V
C
1
]
1

,
_


,
_

.................................................(16)
If the equations (14) and (15) are substitution to the equation (13), ao we can
get the equation:
dV
V
S
dT
T
S
dS
T V

,
_

+
,
_

dV dT
T
C
dS
V

+ .......................................................(17)
dV
T
dT C TdS
V

+
..................................................(18)
2. S as a function of temperature (T) and pressure (p)
In mathematically: S = f (T, p), the total differential is:
dp
p
S
dT
T
S
dS
T
p

,
_

+
,
_

...........................................(19)
If U and V in the combination of The First and The Second Law of
Thermodynamics expressed as a function p and T so:
dp
p
U
dT
T
U
dU
T
p

,
_

+
,
_

........................................(20)
Combination of First And Second Law of Thermodynamic Page 5
By Tenth Group
dp
p
V
dT
T
V
dV
T
p

,
_

+
,
_

..........................................(21)
If the equation (20) and the equation (21) substituted o the equation (4), so
obtained the equation as follow:
1
1
]
1

,
_

,
_

+
1
1
]
1

,
_

+
,
_

dp
p
V
dT
p
V
p dp
p
U
dT
T
U
TdS
T p T
p
dp
p
V
p
p
U
dT
p
V
p
T
U
TdS
T T p
p 1
1
]
1

,
_

,
_

+
1
1
]
1

,
_

+
,
_

dp
p
V
p
p
U
T
dT
T
V
p
T
U
T
dS
T T
p p 1
1
]
1

,
_

,
_

+
1
1
]
1

,
_

+
,
_

1 1
1
1
]
1

,
_

+
,
_


,
_

p p p
T
V
p
T
U
T T
S 1
.....................................(21)
1
1
]
1

,
_

,
_

,
_

T T T
p
V
p
p
U
T p
S 1
....................................(22)
By the return differentiated of partial differential in the equation (21) and the
equation (22), we can get:
p
T
T
p
p
S
T T
S
p
1
1
]
1

,
_

1
1
]
1

,
_

1
]
1

,
_

,
_

+
1
1
]
1

,
_

,
_


1
1
]
1

,
_

+
,
_

,
_

+
p T
V
p
p T
U
T
p
V
p
p
U
T p T
V
p
T
V
T p
U
T
T T
p
2 2
2
2 2
1
1 1
0
1
1
]
1

,
_

,
_


1
1
]
1

,
_

T T
p
p
V
p
p
U
T T
V
T
2
1 1
p
T T
T
V
T
p
V
p
p
U

,
_

,
_

,
_

Where
V
T
V
p

,
_

and
V
p
V
T

,
_

, so obtained:
V T V p
p
U
T

,
_

................................................................(23)
Known that:
V p C
T
U
p
p

,
_

...................................................................(24)
Combination of First And Second Law of Thermodynamic Page 6
By Tenth Group
By substituted the equation (23) to the equation (22), so we get:
1
1
]
1

,
_

,
_

,
_

T T T
p
V
p
p
U
T p
S 1
( )
1
1
]
1

,
_

,
_

T T
p
V
p V T V p
T p
S

1
( ) [ ] pKV V T V p
T p
S
T

,
_


1
V
p
S
T

,
_

...............................................................(25)
If the equation (24) substituted to the equation (21), we get:
1
1
]
1

,
_

+
,
_


,
_

p p p
T
V
p
T
U
T T
S 1
[ ] V p V p C
T T
S
p
p
+
,
_

1
T
C
T
S
p
p

,
_

...................................................................(26)
If the equation (25) and (26) substituted to the equation (19), so we can get:
dp
p
S
dT
T
S
dS
T
p

,
_

+
,
_

Vdp dT
T
C
dS
p
......................................................(27)
Vdp T dT C TdS
p

...................................................(28)
3. S as a function of pressure (p) and volume (V)
The combination of The First and The Second Law of Thermodynamics
provided that:
pdV dU TdS +
. In the differential partial from U against p
and V the independent can be written:
dV
V
U
dp
p
U
dU
p
V

,
_

,
_

. It is
obvious that change the energy in by changes in pressure on the process of
isochoric is:

V
V
C
p
U

,
_

The change internal energy by the change volume on the isobaric is


Combination of First And Second Law of Thermodynamic Page 7
By Tenth Group
p
V
C
V
U
p
p

,
_

So,
dV p
V
C
dp
C
dU
p
V

,
_

If dU subsituted to the combination of The First and The Second Law of


Thermodynamics, so can obtained:
TdS dU pdV +
pdV dV p
V
C
dp
C
TdS
p
V
+

,
_

dV
V
C
dp
C
TdS
p
V

+
................................................(29)
dV
V T
C
dp
T
C
dS
p
V

+
................................................(30)
C. Entropy Ideal Gas and Gas Van der Walls
The equations dV dT
T
C
dS
V

+ , Vdp dT
T
C
dS
p
, and
dV
V T
C
dp
T
C
dS
p
V

+
can be used to calculate the entropy change between two
equilibrium. If ideal gas system already known C
p
and C
V
only a function of
temperature,
T
1

,
p
1

, then each of the equation above would be:


dV dT
T
C
dS
V

+
( )
dV
p
T
dT
T
C
dS
V

,
_

+
1
1
dV
T
p
dT
T
C
dS
V
+
For Ideal Gas:
V
nRT
p
Combination of First And Second Law of Thermodynamic Page 8
By Tenth Group
( )
dV
T
V
nRT
dT
T
C
dS
V
+
V
dV
nR dT
T
C
dS
V
+
If the initial state of the system stated the temperature = T
0
, Pressure = p
0
,
volume = V
0
, entropy = S
0
, and the final state of the expressed by the temperature =
T, pressure = p, volume = V, entropy = S,

then by integrating with the equation
above, we can obtained:
V
dV
nR dT
T
C
dS
V
+

+
V
V
T
T
V
S
S
V
dV
nR dT
T
C
dS
0 0 0

+
V
V
T
T
V
S
S
V
dV
nR dT
T
C dS
0 0 0
1
0 0
0
ln ln
V
V
nR
T
T
C S S
V
+ +
...................................................(31)
Vdp dT
T
C
dS
p

Vdp
T
dT
T
C
dS
p

,
_

+
1
dp
T
V
dT
T
C
dS
p
+
For Ideal Gas:
p
nRT
V
dp
T
p
nRT
dT
T
C
dS
p

,
_

+
p
dp
nR dT
T
C
dS
p
+
If the initial state of the system stated the temperature = T
0
, pressure = p
0
,
volume = V
0
, entropy = S
0
, and the final state of the expressed by the temperature =
Combination of First And Second Law of Thermodynamic Page 9
By Tenth Group
T, pressure = p, volume = V, entropy = S,

then by integrating with the equation
above, we can obtained:
p
dp
nR dT
T
C
dS
p
+

+
p
p
T
T
p
S
S
p
dp
nR dT
T
C
dS
0 0 0

+
p
p
T
T
p
S
S
p
dp
nR dT
T
C dS
0 0 0
1
0 0
0
ln ln
p
p
nR
T
T
C S S
p
+ +
......................................................(32)

dV
V T
C
dp
T
C
dS
p
V

+
dV
V
T
T
C
dp
T
T
p
C
dS
p
V
1 1
1
+
dV
V
C
dp
p
C
dS
p
V
+
V
dV
C
p
dp
C dS
p V
+
If the initial state of the system stated the temperature = T
0
, pressure = p
0
,
volume = V
0
, entropy = S
0
, and the final state of the expressed by the temperature =
T, pressure = p, volume = V, entropy = S,

then by integrating with the equation
above, we can obtained:
V
dV
C
p
dp
C dS
p V
+

+
V
V
p
p
p
V
S
S
V
dp
C dp
p
C dS
0 0 0
1

+
V
V
p
p
p
V
S
S
V
dp
C dp
p
C dS
0 0 0
1
0 0
0
ln ln
V
V
C
p
p
C S S
p V
+ +
......................................................(33)
Combination of First And Second Law of Thermodynamic Page 10
By Tenth Group
The equations (31), (32), and (33) are equivalent. If the system is to be
reviewed gas Van der Waals, known
2 3
3
) ( 2
) (
b v a RTv
b v Rv



and
2 3
2 2
) ( 2
) (
b v a RTv
b v v


, by using the equation (18) expressed in specific quantity is
dV
T
dT c Tds
v

+
, so we can get the equation:
dV
T
dT c Tds
v

+
T
dV
T
dT c
ds
v

dv
b v a RTv
b v v
b v a RTv
b v v R
T
dT
cv ds
2 3
2 2
2 3
2
) ( 2
) (
) ( 2
) (

,
_

+ , so:


+

+
T
T
v
v
v
s
s
v
b v
dv
R
T
dT
c ds
b v
dv
R
T
dT
c ds
0 0 0
If c
v
constant as long as the temperature interval T
0
to T, so the results of the
above integral is:
b v
b v
R
T
T
c s s
v

+
0 0
0
ln ln
....................................................(34)
So it is clear that the constant a on the equation of State gas Van der Waals
does not affect the change of entropy.
D. Potential Thermodynamics
It has been known a hydrostatic system, such as a gas has a number of
coordinates that is quantity that can give illustrate of a macroscopic state. Already
introduced p, V, T, and S, and is known also that the system state can be written with
Combination of First And Second Law of Thermodynamic Page 11
By Tenth Group
two coordinates that are free, in other words each coordinate can be expressed as a
function of two others coordinates
Through the first law of thermodynamics have introduced a quantity of
energy that is in the system (U), where U is a state function of system so that can be
expressed as a function of two coordinates. However, U has what is called natural
coordinates, namely S and V. It can be seen from the first law of Thermodynamics
pdV q d dU
. If the process is reversible, then this natural law can be written:
pdV TdS dU
, so
) , ( V S f U
. Apparently the properties of pure substances
besides can be described by the function U, can also be described by three other
energy functions, namely enthalpy (H), the Helmholtz free energy (F) and Gibbs free
energy (G). The third of this energy is a function of the system state and with U is
called Potential Thermodynamic of a system, each highlighting particular properties
of a process. As with U, other potential Thermodynamics also has its natural
coordinates are discussed as follows.
1. Helmholtz Function (F)
Helmholtz function (often also referred to as the Helmholtz free energy)
is defined as energy in the system reduced the time and temperature with
entropy in mathematics can be formulated:
TS U F
.....................................................................
(35)
In the process of infinite equation (35) can be written
dT S dS T dU dF
. From the combination of first and second law
of Thermodynamic obtained equations
pdV dU dS T
. By substitute
this equations to equation (35), then obtained equations below:
pdV dT S dF
........................................................
(36)
Then, it can be said to be T and V natural coordinates of Helmholtz
function (F). If the isothermal process, dT = 0 then equations (36) can be
written such as below:
pdV dF
....................................................................
(37)
Thus, the total effort on isothermal process is similar to the Helmholtz
energy change. Equation (37) States if W positive (the system does
work), then the Helmholtz energy decreases and vice versa. A major part
Combination of First And Second Law of Thermodynamic Page 12
By Tenth Group
of the Helmholtz function is in statistical mechanics that relates closely to
the partition function Z is defined as:

kT
i
i
e g Z
/
with
i
and g
i
stated in a row value of energy and degeneration different
levels of energy of particle system. Because;
pdV dT S dF
Entropy and pressure can be calculated using simple differential:
V
T
F
S
,
_


dan
T
V
F
p
,
_


2. Gibbs Function (G)
Gibbs function is defined as the difference in enthalpy to the product
temperature and entropy, mathematically represented by the equation:
TS H G
....................................................................
(38)
Already known
pV U H +
, by substitute this equation to equation (38)
obtained equations below:
TS pV U G +
In the equation of infinite, then the above equation becomes:
dT S dS T dp V dV p dU dG + +
........................
(39)
From the combination of first and second law of Thermodynamic
obtained equations
pdV dU dS T +
.
If equations above substitute to equation (39) then obtained equation
below:
dT S dS T dp V dS T dG +
dT S dp V dG
.........................................................
(40)
So, a natural coordinate G is p and T.
3. Enthalpy (H)
Enthalpy is a term used in thermodynamics which stated the amount of
internal energy of a thermodynamic system plus the energy used to do
work. Already known H is a function of the State system, and is
expressed by the equation
pV U H +
. In the process of infinite can be
Combination of First And Second Law of Thermodynamic Page 13
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written
dp V dV p dU dH + +
, where q = dU + pdV. So dH = Q +
Vdp ..(41)
By dividing both sides of equation it with dT, we obtained:
dT
dp
V
dT
Q d
dT
dH
+
on p constant,
p
p p
c
dT
Q d
dT
dH

,
_

,
_

....................................................(42)
Because dH = Q + Vdp, enthalpy change during the process of moving
along the same heat were moved. By applying the combination of first
and second law of Thermodynamic, the equation above can be written as:
dp V dS T dH +
.........................................................(44)
E. Maxwell's Equations
It is well known that the nature of the pure substances can easily be expressed
in four functions:
Internal Energy U,
Enthalpy H = U + pV
Helmholtz function F = U TS
Gibbs function G = H - TS
Each function that can be thought of as a function of p, V and T. Suppose U
and S both can be expressed as functions of V and T, so:
U = function (V, T) and S = function (V, T).
The second equation solved for T is expressed in S and V; with enter a value
of T in the first equation, then obtained:
U = function (S, V).
In a similar way can be continued and said that one of the eight quantities p,
V, T, S, U, H, F, and G can be express as function from other spouse.
Imagine a hydraulic system underwent a process of invertible infinitesimals
from one equilibrium to another State.
1. The internal energy change by:
pdV Q d dU
Combination of First And Second Law of Thermodynamic Page 14
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pdV TdS
with U, T, and p viewed as a function of S and V.
2. Enthalpy change by:
Vdp pdV dU dH +
Vdp TdS +
with H, T, and V viewed as a function of S and p.
3. Helmholtz function change by:
SdT TdS dU dF
pdV SdT
with F, S, and p viewed as a function of T and V.
4. Gibbs function change by:
dG = dH T dS S dT
= -S dT + V dP
with G, S, and V everything is viewed as a function of T and P.
Because U, H, F, and G It is the actual function, differential thoroughly is
dz = M dx + N dy,
with z, M, and N is a function of x and y. So
y
x
x
N
y
M

,
_

,
_

By applying this result in differential thoroughly dU, dH, dF and dG, we get
1.
;
S V
T p
dU TdS pdV So
V S

_ _



, ,
2.
;
p
S
T V
dH TdS Vdp So
p S
_ _
+


,
,
3.
;
T V
S p
dF SdT pdV So
V T
_ _



, ,
4.
;
p
T
S V
dG SdT Vdp So
p T
_ _
+


,
,
So the result of fourth function equation above is known as Maxwell's
equations. The equation does not refer to a process but expressing a relationship in
force at each equilibrium of hydrostatic system.
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Maxwell relations are very useful because it presents the relationship between
the quantity that can be measured and the quantity cannot be measured or is difficult
to measure. For example the four Maxwell relations,
,
p
T
T
V
p
S

,
_

,
_

Maxwell relations are very useful because it presents the relationship between the
quantity that can be measured and the quantity cannot be measured or is difficult to
measure. For example the four Maxwell relationships


from pure substances
according to the following way. If pure substances be used also for isotherm and if
you can't reset a molecular extraordinary (such as the Association or dissociation),
then the molecule would occupy a volume that is smaller so that it is in a more
regular basis. In information theory, our knowledge about this molecule increases. So
entropy decreases and derivatives
T
p
S

,
_

negative. So
,
p
T
V

,
_


positive and it must
have a coefficient from the positive.
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REFERENCE
Hadi, Dimsiki. 1993. Termodinamika. Jakarta: Departemen Pendidikan Dan
Kebudayaan Derektorat Jendral Pendidikan Tinggi Proyek Pendidikan
Tenaga Guru.
Rapi, K. 2009. Buku Ajar Termodinamika. Singaraja.
Zemansky, Mark W. & Dittman, Richard H. 1986. Kalor dan Termodinamika.
Bandung: ITB.
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