State of a gas can be described by its variables: n, P,T,

and V.

For a fix amount of gas (n is fixed), now the variables : P, T
and V. P&V relate to mechanical and T by heat.

Mathematically : f(P,V,T) = constant

U is a state function, then U = U(P,V,T)

3x10
23
coordinates to solve the problem. Therefore, we
choose any 2

eg U = U(P,V) fix T U = U(V,T) fix P etc.


Suppose U = U(P,V) constant T

The Partial differential equation :



What does it means?

Take F = F(x,y)
Then:


F = F(x,y) exists if:



F is a state function F = F(x,y) and dF is called exact differential


dV
V
U
dP
P
U
dU
P V
|
.
|

\
|
c
c
+
|
.
|

\
|
c
c
=
, ) y , x ( F F =
dy
y
F
dx
x
F
dF
x
y
|
|
.
|

\
|
c
c
+
|
.
|

\
|
c
c
=
|
|
.
|

\
|
c c
c
=
|
|
.
|

\
|
c c
c
x y
F
y x
F
2 2
selanjutnya dF ditulis

(1.33)
Ada fungsi keadaan ini [F = F (x,y)] dengan syarat:


if , F F(x,y), dF is inexact differential


Consider dz = M(x,y)dx + N(x,y)dy in the form of




by comparing and

therefore



in the form of




|
|
.
|

\
|
c c
c
=
|
|
.
|

\
|
c c
c
x y
F
y x
F
2 2
dy
y
F
dx
x
F
dF
x
y
|
|
.
|

\
|
c
c
+
|
.
|

\
|
c
c
=
y
x
F
M
|
.
|

\
|
c
c
=
x
y
F
N
|
|
.
|

\
|
c
c
=
=
|
|
.
|

\
|
c
c
x
y
M
y
x
N
|
.
|

\
|
c
c
|
|
.
|

\
|
c c
c
=
|
|
.
|

\
|
c c
c
x y
F
y x
F
2 2
Choose U = U(V,T) and dU = dq + dw

at constant V we get then





Define :


where C
V
called heat capacity at constant V

C
V
= a + bT + cT
2
+ ( temperature dependence)

C
V,m
= C
V
/n called molar heat capacity



4
V V
T
U
dT
dq
|
.
|

\
|
c
c
=
|
.
|

\
|
V
V V
C
T
U
dT
dq
=
|
.
|

\
|
c
c
=
|
.
|

\
|
dT
T
U
dq
V
V
|
.
|

\
|
c
c
=
Choose U = U(P,T) and first law followed by V = V(P,T)

we then define:

,heat capacity at constant P


C
P
= a + bT
2
+ cT
3
+ . temperature dependence



5
P
P
dT
dq
C
|
.
|

\
|
=
n
C
P
= C
P,m
=molar heat capacity at P constant
For ideal gas:

C
P
C
V
= nR

Monoatomic molecule C
v
= 1.5 R
Diatomic molecule C
v
= 2.5 R

For any gas :
6
P T
v P
T
V
V
U
P C C
|
.
|

\
|
c
c
(

|
.
|

\
|
c
c
+ =
Define H = U + PV

dH = d(U + PV) and first law

dH = dq + VdP

at constant P dH = dq

therefore


dH
P
= dq
P
or

H = q


7
P
P P
C
dT
dq
dT
dH
=
|
.
|

\
|
=
|
.
|

\
|
Ideal gas fullfil the following conditions

i) state equation PV = nRT and

ii)
0
V
U
T
=
|
.
|

\
|
c
c

Joule measured temperature changes
when ideal gas expand adiabatically into a
vacuum.

The result observed that,
no temperature change

adiabatic : q = constant
dq = 0 therefore q = 0

No work is done, P
ext
= 0 and dw = 0, w =0

First law dU = dq + dw = 0 + 0 = 0
Conclusion : w = 0
q = 0
U = 0


9
Ideal
Gas
(1)
Vacuum
(2)
thermometer
insulator
Figure :Joule Experiment
valve
Consider U = U (V, T):




experiment data : dT = 0, dU = 0 therefore



and dV 0 , therefore



is called internal pressure

10
0
V
U
T
=
|
.
|

\
|
c
c
dT
T
U
dV
V
U
dU
V T
|
.
|

\
|
c
c
+
|
.
|

\
|
c
c
=
dV
V
U
0
T
|
.
|

\
|
c
c
=
T
V
U
|
.
|

\
|
c
c
= 0 for ideal gas
= small for other gas
= large for solid and liquid

Question :


Results obtained from Joules experiment was not
satisfied due to heat capacity of water is very much
larger than gas, hence small change in temperature
difficult to detect.


T
V
U
|
.
|

\
|
c
c
? 0
P
U
T
=
|
.
|

\
|
c
c
Adiabatic process, q = 0, therefore AU = w (First Law of
Thermodynamic)

Compartment A: w
A
= P
A
V
A

Compartmen B: w
B
= -P
B
V
B

w
total
= w
A
+ w
B

= P
A
V
A
+ (- P
B
V
B
)
However,
AU = U
B
- U
A
= w
total


U
B
- U
A
= P
A
V
A
+ (- P
B
V
B
)
U
B
+ P
B
V
B
= U
A
+ P
A
V
A


H
B
= H
A

H
B
H
A
= AH = 0
Process occurs at constant enthalpy.


12
Thermometer
A
P
A

B
P
B

T
1
T
2

Porous plate
insulator
insulator
compressed expanded
H = U + PV
T detected, means cooling process
occurs during gas expansion.
Joule-Thompson coefficient, can be
measured



During gas expansion, if the sign of :
positive cooling
negative heating
zero no cooling & heating

Temperature during expansion which = 0
is called the inversion temperature.
Application: A gas can be used as a
refrigerant only at temperature below the
maximum inversion temperature, which is
607 K for N
2
, 204 K for H
2
and 43 K for He.



13
P
T
P
T
H
A
A
~
|
.
|

\
|
c
c
=
600-
500-
400-
300-
200-
100-
700-
| | | | |
10 20 30 40 50
0- |
0
cooling heating
Critical point
P (mPa)
T (K)
Isenthalps and inversion temperature for N
2

Using cylic rule:

P
T
P
T
H
C
P
H
T
H
P
H
P
T
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
=




15
dV
V
nR
T
dT C
V
. =
|
.
|

\
|
=
V
nRT
P
dV
V
nR dT
T
C
V
V
T
T
v
} }
=
2
1
2
1
1 1
1
2
1
2
ln ln
V
V
nR
T
T
C
v
=
(a)







(b)




(c)
16
V
P
C
C
=
V
C
nR
= 1 nR C C v P =
1
2
1
1
2

|
|
.
|

\
|
=

V
V
T
T

|
|
.
|

\
|
=
2
1
1
2
V
V
P
P

1
1
2
1
2

|
|
.
|

\
|
=
P
P
T
T
nR
V
C
nR
V
C
2 2 1 1
T V T V =

2 2 1 1
V P V P =

=
1
2 2
1
1 1
P T P T
or
or
or
Heat effect during chemical and physical change

1. Constant Volume
q
V
= U ( from first law)

2. Constant Pressure
q
P
= H ( from dH = dq + VdP)

3. Chemical Reaction

Reactant Product
H

H = U + (PV) where
(PV) = (PV)
product
(PV)
reactant




17
Case:

1. All products and reactants in solid or liquid phase, (PV)
very small, hence H U so q
P
q
V


2. If gas(gaseous) involved, (PV) depends on the n
g
:

n
g
= n
g(product)
n
g(reactant)
.

For ideal gas
(PV) = n
g
RT
so
H = U + n
g
RT



18
The combustion of ethanol in a constant-volume calorimeter produces 1364.34 kJ
mol
-1
at 298 K. what is the value of H for the following combustion reaction?

C
2
H
5
OH(l) + 3O
2
(g) 2CO
2
(g) + 3H
2
O (l)



19
ANSWER

H = U + RT(n)

(n) = 2 - 3 = -1

Thus,

H = -1364.34 kJ mol
-1
x (8.314 JK
-1
mol
-1
x 298 K x -1)

= - 1366.82 kJ mol
-1

20
All state functions obey Hess Law (X = U, H, S, G and
A ; all are exact differential).
The values depend on the final and initial states

aA + bB mM + nN

at particular T:

H
T
= ( H
T(product )
- H
T(reactant)
)

a) for two temperatures, T
1
and T
2
at constant P:



integrate limit between T
1
and T
2
:
H
2
H
1
= C
P
dT where

H
2
at T
2
and H
1
at T
1

if T
1
and T
2
not much different, C
P
assume to be constant, then
H
2
H
1
= C
P
(T
2
T
1
)


( ) ( ) ) t tan ac (Re C ) product ( C
T
H
P P
P
T
E E =
|
.
|

\
|
c
A c
b) With phase change
H

from A to D ?
Apply Hess law
A to B + B to C + C + C to D + D


T
1
T
m
T
2
T
Liquid
Gas
Solid
D
A
B C
P
2

P
1

Phase changes for a component