Chapter 2

The first law of thermodynamics

thermodynamics deals with (a) energy
conversion and (b) direction of change.
Two laws, the first law and the second law
of thermodynamics, are foundation of
thermodynamics.
They are an experience summary of human
beings in long history, therefore can not be
proved mathematically, while their
correctness is indubitable.
2.1 Concept and nomenclature in
thermodynamics
2.1.1 System and surroundings

Three kinds of systems
Open systems:
exchange of both matter and
energy

Closed systems:
no exchange of matter but
some exchange of energy.
Isolated systems:
neither exchange of matter
nor exchange of energy.
2.1.2 Extensive property and
intensive property
Extensive property
its value depends on the extent or size of the
system. The overall value is the sum of various
parts of the system.
For example, m, V, U, etc.
Intensive property
Its value is independent of the extent or size of the
system.
For example, T, c, , etc.
any extensive variable divided by the moles or
mass becomes an intensive variable.
2.1.3 State and state function
State

(2004

State function
a property of a system that is not dependent
on the way in which the system gets to the
state in which it exhibits that property.
Two properties of state functions
(1) the infinitesimal changes of a state
function can be expressed in total
differential. e.g. z=f(x,y)


(2) Any changes between the initial and
final states depend only on the state of the
system not on the paths through which the
change takes place.
y
x
z z
dz dx dy
x y
| | c c
| |
= +
| |
c c
\ .
\ .


T=T2T1 U=U2 U1
Y=Y2Y1 X=X2X1

A
B
X
Y
2.1.4 Equilibrium state
three conditions have to be necessary to an
equilibrium state:
(A) Thermal equilibrium
(B) Mechanical equilibrium
(C) Chemical reaction and phase
transition equilibrium
2.1.5 Steady state
Steady state is a situation in which all state
variables are constant in spite of ongoing
processes that strive to change them.

It is different from the equilibrium state.
2.1.6 Process and path
Process is a change of a system from initial state
to finial state.
Path is the intermediate steps between the initial
state and the final state in a change of state.
Isobaric: process done at constant pressure,
p
1
=p
2
=p
sur
.
Isochoric: process done at constant volume,
V
1
=V
2
.
Isothermal: process done at constant temperature,
T
1
=T
2
=T
sur
.
Adiabatic: process where Q = 0, that is, no heat
exchanges
Cyclic: process where initial state = final state.
Spontaneous and non-spontaneous
A spontaneous process is one that will naturally
occur in the absence of external driving forces.
For example, a ball rolls off a table and falls to the
floor.
A non-spontaneous process is the reverse of a
spontaneous process. This does not mean that non-
spontaneous processes do not happen. They
simply do not happen by themselves.
2.1.7 Heat and work
Heat (Q) is the exchange of thermal energy from a
hot body to a cold body. It is a kind of energy
transferred in a driving force of temperature
difference.
the zeroth law of thermodynamics
If two bodies are in thermal equilibrium with a
third body, they are also in thermal equilibrium
with each other.
Sign Convention for heat Q
Positive heat in, negative heat out.
Endothermic Q>0, exothermic Q<0.
Example Hold a piece of ice in your hand until it
melts
Solution A
SystemYou
SurroundingsIce + the rest of the universe
Q < 0Heat flows out of the system (you) into
the ice.
Solution B
SystemIce
SurroundingsYou + the rest of the universe
Q > 0Heat flows into the system (ice) from you.
Example
H
2
burns in a heat insulated (adiabatic)
container filled with O
2
. what is the heat
sign of this process? Positive, negative, or
zero?
Work
Work (W): All the transferring form of
energy except heat.
There are several kinds of work. Pressure-
volume (pV) work, electrical work, surface
work, and mechanical work, etc.
non-volume work (W): Except pressure-
volume work, all the other works.
Work sign
W>0
W<0


According to this convention heat and
work are both taken as positive when their
direction is into the system of interest. Heat
and work are negative when they are out of
the system of interest.
Sign of heat and work
The common properties of heat and
work
1. Both are only recognized at the boundaries of a
system as they cross the boundaries.
2. Systems possess energy, but not heat or work.
We can say a process has done some work, but we
can not say a state has done some work.
3 Both heat and work are not function of state,
they can not be expressed in total differential. The
infinitesimal changes are denote by Q and W
instead of dQ and dW, respectively. Their
magnitudes depend on the path
Computation of pV work
ex
W p dV o =
}

= =
2
1
2
1
V
V
ex
V
V
dV p W W o
2
1
V
ex
V
W p dV =
}
2.1.8 Reversible pressure-volume
work
Reversible process
is one in which the timescale is assumed to be so
slow that every intermediate state deviates only
infinitesimally from equilibrium.
After it has taken place, the process can be
reversed and causes no change in either the system
or its surroundings. That is, all properties of both
system and surroundings must be recovered to
their original states. There must be no net work or
heat.
It is only an ideal process, does not exist in real
world.
An example of reversible process
Reversible
process would be
realized by
removing the sand
one grain at a time
irreversible process
An irreversible process
is a process that cannot return both the system and
the surroundings to their original conditions. That
is, the system and the surroundings would not
return to their original conditions if the process
was reversed.
In irreversible process the intermediate states
cannot be specified by any set of macroscopic
variables and which are not equilibrium states.
All the really happened processes are irreversible
processes.
An Irreversible Process


Reversible pressure-volume work
For ideal gas
2
1
(reversible = )
V
ex
V
W pdV p p dp =
}
2
1
(ideal gas)
V
V
nRT
W dV
V
=
}
1
2
2
1
ln ( constant)
V
V
V dV
W nRT nRT T
V V
= = =
}
2
1
ln (ideal gas, reversible expansion, const)
V
W nRT T
V
= =
pV work
expansion work
Fig 2.1.4 Three-step expansion of ideal gas at
constant temperature
in a reversible process

The surroundings actually
obtained the maximum work
from system.
Fig 2.1.5 Three-step compression of ideal gas at
constant temperature
in a reversible process

The surroundings actually gives
the minimum work to system
The system gives the maximum
work to surroundings.
Example
Calculate the work for the isothermal
reversible of 1 mol of an ideal gas at 300K
from an initial volume of 20 dm
3
to a final
volume of 40 dm
3
.
Solution
2
1
40
ln ln 1728 J
20
V
W RT RT
V
= = =
2.1.9 Thermodynamic energy
Thermodynamic energy, also called
internal energy
the energy associated with the random,
disordered motion of molecules or particles.
It is separated in scale from the macroscopic
ordered energy.
Its absolute value is unknown.
Its symbol and unit are U and joule
respectively.
2.1.10 Temperature scales

2.1.10 Temperature scales
Celsius scale (formerly called the
centigrade scale)
the ice and steam points were originally
assigned the values of 0 and 100C,
respectively.
Fahrenheit scale
The corresponding values on the Fahrenheit
scale are 32F and 212F
T/=1.8T/+32
thermodynamic temperature scale
(K)
Does a temperature has an absolute zero, or 0 K?
From the thermal motion of molecules, it should be at
0K if the motion freeze.
From pV=nRT we can see that there is a naturally-
defined zero on this scale. p0 T0.
one other fixed point need be defined. its value is set as
273.16 K at the triple point of water.
This is known as the ideal gas temperature scale. It is
identical to Kelvin temperature scale based on Carnot
heat engine in Chapter 3.
2.1.11 Standard state
Standard state is a state of a system chosen as
standard for reference by convention.
p = p

= 100 kPa
Standard state of gases:
the state of the pure substance in the gaseous
phase at the standard pressure p = p

= 100 kPa,
assuming ideal behavior.
condensed phase:
the state of the pure substance in the liquid or solid
phase at the standard pressure p = p

.
a solute in solution
the state of solute at the standard molality
b

=1mol kg-1, standard pressure p

=100 kPa or
standard concentration c

= 1mol dm-3 and

exhibiting infinitely dilute solution behavior.
Solvent in solution or component in liquid
mixture
Standard state: Pure liquid at 100kPa
The standard state of a system can be defined at
any given temperature.
a few texts (especially in related disciplines such
as physics and engineering) use 0 degrees Celsius
for Standard Temperature and Pressure (STP).
2.2 The first law of
thermodynamics
2.2.1 The first law of thermodynamics



W should include all kinds of work.
The other parlance about the first law of
thermodynamics is that a perpetual
motion machine of the first kind can not
work.
dU Q W o o = +
U Q W A = +
2.2.2 Heat and enthalpy
Heat depends on the path in which a process
takes place.
Q
V
symbolizes the heat at constant volume.
Q
p
symbolizes the heat at constant pressure.
If we assume that W=0, then at constant
volume W = pdV =0.
Q
v
= U - W
Q
v
= U=U
2
-U
1
Heat at constant pressure
If we assume that W=0, then at constant pressure
Q
p
= U - W
Q
p
= U + pV (p
1
= p
2
= p
ex
)
Q
p
= U
2
- U
1
+ p (V
2
-V
1
)
Q
p
= U
2
- U
1
+ pV
2
- pV
1
Q
p
= U
2
+ pV2 - U
1
- pV
1
Q
p
= (U
2
+ pV
2
) - (U
1
+ pV
1
)
Define U + PV = H, which is called enthalpy.
It is a state function in Joule. Absolute value and
physical meaning unknown.
2.2.3 Joules experiment
Q=0, W=0. Then
UQW0


Since dT = 0, it follows that

For ideal gases at constant temperature


H=f(T)
0
T V
U U
dU dV dT
V T
c c
| | | |
= + =
| |
c c
\ . \ .
0 dV = 0
T
U
V
c
| |
=
|
c
\ .
H U pV U nRT = + = +
2.2.4 Molar heat capacity
heat capacity: C(T)= Q/dT
dT
Q
n
T C
m
o 1
) ( =
dT
dU
n dT
Q
n n
T C
C
V V
m V
1 1 ) (
,
= = =
o
dT
dH
n dT
Q
n n
T C
T C
p p
m p
1 1
) (
) (
,
= = =
o
2
,
1
( )
T
V V m
T
Q U nC T dT = A =
}
2
,
1
( )
T
p P m
T
Q H nC T dT = A =
}
For ideal gases
2
1
T
,
T
p p m
H nC dT A =
}
2
,
1
( )
T
V m
T
U nC T dT A =
}
These two equation are valid for the calculation of
enthalpy change or thermodynamic energy change
in any process, constant pressure or constant
volume is no more a condition for ideal gases.
2.2.4.3 Relation between C
V
and C
p
( )
from

p V
p V V
p
p p V
V T
U pV
H U U
C C
T T T T
U V U
p
T T T
U U
U f T V dU dT dV
T V
p
c +
c c c
| | | | | |
= =
`
| | |
c c c c
\ . \ . \ .
)
c c c
| | | | | |
= +
| | |
c c c
\ . \ . \ .
c c
| | | |
= = +
| |
c c
\ . \ .
,
at const ant , di f f er ent i at e t hi s equat i on and obt ai n

Substitute into the first euqation
p
P V
T
V T
p
p
p
U U U V
T T V T
U
T
U V
C C p
V T
c c c c
| | | | | | | |
= +

( c c
| | | |
= +

| | | |
c
| | (
c c
\ . \ .

c c c
\ . \ . \ . \ .
c
| |
|
c
\ .

P V
T p
U V
C C p
V T
(
c c
| | | |
= +
| | (
c c
\ . \ .

The first term indicates the increase of U, and the
second volume work.
For ideal gas



For condensed phase
, ,
( ) ( )
0;
; or
T p p p
p V p m V m
U V pV nRT
p nR
V T T T
C C nR C C R
c c c c
| | | | | | | |
= = = =
| | | |
c c c c
\ . \ . \ . \ .
= =
0;
p V
p
V
C C
T
c
| |
~ ~
|
c
\ .
Heat capacities of ideal gases
Equipartition of Energy Theorem states that
molecules in thermal equilibrium have the same
average energy associated with each independent
degree of freedom of their motion and that the
energy is (1/2)RT per mole.
For a monoatomic ideal gas
3
, 2 V m
C R =
For a diatomic ideal gas
5
, 2 p m
C R =
5
, 2 V m
C R =
7
, 2 p m
C R =
2.2.4.4 Temperature dependent
of molar heat capacity
By suming up huge number of experiments, C
p,m
f(T)
is ordinary expressed as
C
pm
= a + b T + c T
2

C
pm
= a + b T + cT
2

C
pm
= a + b T + c T
2
+ d T
3

abcdc are all constats which can be
found in appendix D in our textbook.
Pay special attention on the valid temperature
ragne for the calculation of C
p
by using these
constants.
average molar heat capacity at constant pressure:
( )
( )
( ) ( )
2
1
2
2 2 3 3
2 1 2 1 2 1

2 3
T
p
T
Q n a bT cT dT
b c
na T T n T T n T T
= + +
= + +
}
2
1
,
,
2 1 2 1
T
p m
T p
p m
C dT
Q
C
T T T T
= =

}
The average molar heat capacities apply to two cases:
(1) Rough computation of heat
(2) temperature change range is samll.
Theat capacities of gaseous mixture
B m V B A m V A V
C y C y C
, , , ,
+ =
B m p B A m p A p
C y C y C
, , , ,
+ =
y is mole frction of compents of gaseous mixture.
2.2.5 Reversible adiabatic process of
an ideal gas
From the first law: dU = Q + W
For the reversible adiabatic process Q = 0.

for ideal gases





is called ratio of heat capacity or adiabatic
index.
dU W pdV o = =
, V m
dU nC dT = / p nRT V =
,
( / )
V m
nC dT nRT V dV =
, V m
dT R dV
T C V
=
, , ,
, , ,
1 where =
p m V m p m
V m V m V m
C C C
R
C C C

= =
Using the ideal gas law to replace V, we get
the other two equations
( 1)
dT dV
T V
=
2 2
1 1
ln -( -1) ln
T V
T V
=
1
2 1
1 2
T V
T V

| |
=
|
\ .
1
2 2
1 1
T p
T p

| |
=
|
\ .
1 1 2 2
pV p V

=
constant. pV

=
The work done on or take by system is




Integrating this leads to



p
0
, V
0
are pressure and volume of system at
any state.
2 2
1 1
0 0
/
V V
V V
W pdV p V dV V

= =
} }
0 0
1 1
2 1
1 1
1
p V
W
V V

| |
=
|

\ .
0 0
where
p V
p
V

=
0 0 2 2 1 1
1 1 1 1
2 1 2 1
2 2 1 1
1 1 1
1 1
1
p V p V pV
W
V V V V
p V pV
W

| | | |
= =
| |

\ . \ .

The above equation can be changed into a

simple form
W

> W

p
V
A (p
1
,V
1
)
B (p
2
,V
2
)
C (p
3
,V
2
)
V
1

V
2



Comparision of isotherms to adiatats
Example
1mol 25100kPa
50kPaT
2
WUH
Q=0 U=W=-p
amb
V
nC
V,m
(T
2
-T
1
)= -p
2
(V
2
-V
1
)
V
2
=nRT
2
/p
2
V
1
=nRT
1
/p
1
T
2
=255.56K
U=nC
V,m
T=(5/2)R(255.56-298.15)=-885.3 J
H=nC
p,m
T= (7/2)R(255.56-298.15)=-1239 J
H= U+(pV)=U+RT
=-885.3+8.3145(255.56-298.15)=-1239 J
Example: 4 mol p
1
=50kPa, V
1
=160dm
3

p
2
=200kPaT
2
WUH
T
1
=p
1
V
1
/nR=240.53K




T
2
=(p
2
/p
1
)
R/Cp,m
T
1
=357.43K
U=nC
v,m
(T
2
-T
1
)=9.720kJ
H=nC
p,m
(T
2
-T
1
)
W=U
, ,
, , , ,
,
, ,
,
1
2 2 2 2 2
1 1 1 1 1
p m V m
p m V m V m V m
p m
p m p m
V m
C C
C C C C
R
C
C C
C
T p p p p
T p p p p

| | | | | | | |
= = = =
| | | |
\ . \ . \ . \ .
2.3 Phase transformation
phase is a portion of a system that has
uniform properties and composition.
Phase change
Phase change includes
from a liquid to a gas (vaporization)
from a solid to a liquid (fusion)
from a solid to a gas (sublimation)
crystal form transition

, , ,
vap m fus m sub m trs m
H H H H A A A A
Phase change at constant pressure
p
Q H = A
( ) ( ) H H H
|
o
| o A =
/
m
H H n
| |
o o
A = A
The molar change of enthalpy
For melting and crystal transition process at constant
pressure and constant temperature
0
p
Q H W p V U H = A = A ~ A ~ A
For vaporization and sublimation processes
( )
( ) ( )
p
Q H
W p V pV g nRT
U H pV H pV g H nRT
= A
= A ~ ~
A = A A ~ A ~ A
example
10050dm
3

50gQW
UH
vap
H
m
=40.668kJ mol
-1

n mol
n=pV/RT=1.633mol, 29.42g
H=1.63340.668=66.41kJ
W=0
Q=U=H-(pV)=H-pV(g)
=H-nRT=61.34kJ
Temperature dependence of enthalpy
of phase change
1
2
2
1
2 1
,
,
( ) ( ) ( ) ( )
( ) ( )
( ) ( )
m m
T
m p m
T
T
m p m
T
H T H H T H
H C dT
H C dT
| |
o o
o |
o o
| |
A = A + A + A
A =
A =
}
}
2
1
2
1
p,m , ,
,
m 2 m 1 ,
C = ( )-C ( )
( )+ ( )
( ) ( )+
p m p m
T
m m p m
T
T
p m
T
C
H H C dT
H T H T C dT
| |
o o
| o
o |
A
A A = A
A = A A
}
}
2.4 Standard molar enthalpy of
reaction
2.4.1 Stoichiometric coefficients
aA + bB = yY + zZ
0=aAbByY+zZ

= B
B
v 0
The numbers, a, b, y, and z, showing the relative
numbers of molecules reacting, are called the
stoichiometric coefficients.
2.4.2 Extent of reaction
d=dn
B
/
B

for a same reaction, if the equation of
chemical reaction is written in different form,

B
will also be different, and then extent of
reaction will be different too.
For example:
N
2
(g)+3H
2
(g)= 2NH
3
(g)
N
2
(g)+ 3/2 H
2
(g)= NH
3
(g)
2.4.3 Molar enthalpy of reaction
Molar enthalpy of reaction is an enthalpy change
of a reaction.
For example:
aA bB yY zZ + = +
( ) ( )
* * * *
( ) ( ) ( ) ( )
r Y m Z m A m B m
H n H Y n H Z n H A n H B A = + +
*
/ ( )
r m r B m
B
H H H B v A = A A =

r
H
m
is molar enthalpy of reaction; * stands for a pure
substance.
2.4.4. Standard molar enthalpy of reaction
Standard molar enthalpy of reaction:
the enthalpy change per mole for
conversion of reactants in their standard states
into products in their standard states, at a
specified temperature.
( )
r m B m
B
H H B v A =

, , , ,
pure pure pure pure
r m
H
A B L M
T p T p T p T p
A B L M v v v v
A
+ +
!
! ! ! !
2.5 Calculation of standard enthalpy of reactions
2.5.1 Standard molar enthalpy of formation
Standard molar enthalpy of formation
The enthalpy change when one mole of the
compound is formed at 100 kPa pressure and given
temperature from the elements in their stable states
at that pressure and temperature. the stable forms of
the elements have
For example:
f m
H A
2 2
2 2 2 4
2 2 2
C(graphite) + O (g) = CO (g)
H (g) + S( rhombic) = 2O (g) + H SO (l)
2Hg(l) + Cl (g) = Hg Cl (s)

0
f m
H A =
!
-1
2
(CO , g) 393.509 kJ mol
f m
H A =
!
Note that
Any form of elements other than
the most stable will not be zero; C
(diamond), C (g), H (g), and S
(monoclinic) are examples.
Calculation of standard enthalpy of reactions
The same stable
elements in the
same quantities at
standard pressure

H1

H2
r
A B Y Z

- A + - B Y + Z
pure pure pure pure
m
H
p p p p
v v v v
A

!
! ! ! !
1
2
(A) (B)
(Y) (Z)
A f m B f m
Y f m Z f m
H H H
H H H
v v
v v
A = A A
A = A + A
! !
! !
1 2 r m
H H H A + A = A
!
2 1
(Y) (Z) (A) (B)
r m
Y f m Z f m A f m A f m
H H H
H H H H v v v v
A = A A
= A + A + A + A
!
! ! ! !
( )
r m B f m
B
H H B v A = A

! !
Example Calculate the standard enthalpy of following reaction
at 25 by using standard molar enthalpy of formation
(g) H O(g) H 2 (g) H C OH(g) H C 2
2 2 6 4 5 2
+ +
Solution
f m
1
kJ mol
H

C
2
H
5
OH(g) C
4
H
6
(g) H
2
O(g) H
2
(g)
-235.10 110.16 -241.81 0
r m f m 4 6 f m 2
f m 2 5
(C H , g)+2 (H O, g)
2 (C H OH, g)
H H H
H
A = A A
A
1
1
mol kJ 72 . 96
mol kJ )] 10 . 235 2 ( 818 . 241 2 [110.16 =

=

f m 2 f m 2 vap m 2
(H O, g, ) (H O, l, ) (H O, ) H T H T H T A = A +A note
2.5.2 Standard molar enthalpy of combustion
Definition: The enthalpy change when a mole of substance is
completely burnt in oxygen at a given temperature and standard
pressure.

The general convention for the products of combustion is as
follows. Carbon in organic compound becomes CO
2
(g); H becomes
H
2
O(l); N becomes N
2
(g); S becomes SO
2
(g); Cl becomes HCl(aq)
and so on.
All these complete products have an enthalpy of combustion
of zero.
c m
( , ) H B T A
$
For example, under 298.15K and standard pressure:
3 2 2 2
-1
r m
CH COOH(l) 2O (g) 2CO (g) 2H O(l)
870.3 kJ mol H
+ = +
A =
$
-1
c m 3
(CH COOH,l,298.15 K) -870.3 kJ mol H A =
$


H
1
H
2
H
1
= H
m
+ H
2

H
m
= -(H
2
- H
1
)

r m B c m
B
(298.15 K) - (B,298.15 K) H H v A = A

$ $
r m c m c m c m
(A) 2 (B) - (C) H H H H A = A + A A
$ $ $ $
2 3 3 2 2
(COOH) (s) 2CH OH(l) (COOCH ) (s) 2H O(l) + = +
For example
A B C D
Determination of heat of combustion
2.5.3 Dependence of standard molar enthalpy of reaction
on temperature
) (
1 m r
T H

1
H A

2
H A
aA
+
bB
aA
+
bB
yY
+
zZ
yY
+
zZ

3
H A

4
H A
) (
2 m r
T H

A
T, C y H
T
T
p,
(Y)d
2
1
m 3
}
= A

T, C z H
T
T
p,
(Z)d
2
1
m 4
}
= A

( ) ( )
1 1 2 2 3 4 r m r m
H T H H H T H H A = A +A +A +A +A
since
T, C a H
T
T
p,
(A)d
2
1
m 1
}
= A

T, C b H
T
T
p,
(B)d
2
1
m 2
}
= A

then
2
1

2 1 ,

( ) ( ) ( )
T
B
r m r m p m
T
H T H T C B dT v A = A +

}
It is called Kirchhoff equation
2.5.4 The relationship between heat of chemical
reaction at constant pressure and volume
reactions involving only solids or liquids
volume work W0, and (pV)0, then for
solids and liquids QHU.
reactions involving gases
the product pV may be replaced by
B
RT




( )
r m r m B
B
H U RT g v A = A +

( )
p V B
B
Q Q RT g v = +

when ( ) 0, then , or
when ( ) 0, then , or
B r m r m p V
B
B r m r m p V
B
g H U Q Q
g H U Q Q
v
v
= A = A =
= A = A =

2.5.5 Hesss Law and reaction enthalpy

Hesss law states that the enthalpy change
of any reaction may be expressed as the
sum of the enthalpy changes of a series of
reactions into which the overall reaction
may formally be divided.
The enthalpy change of a reaction at
constant pressure or constant volume
depends only on the final and initial states,
and not on the path connecting them.
Example
some reactions can not be studied directly
C(graphite) + 2H
2
(g) CH
4
(g)
Consider following reactions



The combination of these three reactions
from (a)+2(b)+(c), we get the above
studied reaction.
-1
4 2 2 2 ,
-1
1
2 2 2 , 2
2 2 ,
CH (g) + 2O (g) CO (g) + 2H O(l) 890.35kJ mol (a)
H (g) + O (g) H O(l) 285.84kJ mol (b)
C(graphite) + O (g) CO (g) 393.5
r m a
r m b
r m c
H
H
H
A =
A =
A =
-1
1kJ mol (c)
Then

, , ,
2
r m r m a r m b r m c
H H H H A = A + A + A
-1
( 890.35) 2 ( 285.84) ( 393.51)
74.84kJ mol
r m
H A = + +
=

2.5.6 The maximum temperatures of

flames and explosions
The temperature reached for a combustion
reaction at constant pressure and adiabatic
system is known as the maximum
temperature of flame. Q
p
=H=0
the temperature reached for an explosion in
an adiabatic system and at constant volume
is called the maximum temperature of
explosion. Q
V
=U=0
(CH
4
, g)
25(p100kPa)
0.21

(CH
4
,g)
CH
4
(g)+2O
2
(g)CO
2
(g)+2H
2
O(g)
A
r
H
m

A
f
H

A
r
H

m
A
c
H

m
(CH
4
,g)A
r
H

m
CH
4
(g)+2O
2
(g) CO
2
(g)+2H
2
O(g)
CO
2
(g)+2H
2
O(l)
A
r
H

m
A
c
H

m
(CH
4
,g)
vap
H
m
(H
2
O)
A
r
H

m
= A
c
H

m
(CH
4
,g)+ 2A
vap
H
m
(H
2
O)
=802.286kJ
1mol(CH
4
,g)
4mol4/0.210.79mol=15.05mol

T
0
=298.15K
CH
4
(g)1mol,O
2
(g)

4mol
N
2
(g)

15.05mol
T
CO
2
(g)1mol, H
2
O

(g)

2mol
O
2
(g)

2mol,N
2
(g)

15.05mol
T
0
=298.15K
CO
2
(g)1mol, H
2
O

(g)

2mol
O
2
(g)

2mol,N
2
(g)

15.05mol
A
r
H

m
AH
2
Q
p
=AH=0

Q
p
= AH = A
r
H

m
+ AH
2
=0
( ) ( ) ( ) ( ) { } T C C C C H
T
T
p p p p
d g , N 05 . 15 g , O 2 g O, H 2 g , CO
0
2 m , 2 m , 2 m , 2 m , 2
}
+ + + = A
CO
2
(g) , H
2
O(g)

,O
2
(g)

,N
2
(g)
C
p,m
= a+bT+cT
2

A
r
H

m
+ AH
2
= 0 T
T =1477K

2.6 Joule-Thomson effect
The experiment by Joule and Thomson showed that H of
a real gas is not only the function of T, but also the function
of p.
1 The experiment by Joule and Thomson
p1,V1,T1 p2,V2,T2
Porous plug
Adiabatic wall
thermometer
throttle expansion

p
1p
2

1 1
W p V = A


Q=0
2 1
U U U W =A =

2 2
W p V = A
1 1 1 1
( =0 ) pV V V V = A =
2 2 2 2
( = 0 ) p V V V V = A =


1 2 1 1 2 2
W W W pV p V = + =

2 1 1 1 2 2
U U pV p V =

A
H = 0
2 1
H H =

2 2 2 1 1 1
U p V U pV + = +
2. -
>0
T - J

J-T
( )
H
T
p

c
=
c
T - J

<0
T - J

=0
-Joule-Thomson coefficient),

Show that for ideal gases

H= f ( T, p)
0 =
T J

( ) ( ) 0
p T
H H
dH dT dp
T p
c c
= + =
c c
( ) ( )
( )
( )
T T
J T H
p
P
H H
T p p
H
p C
T

c c
c c c
= = =
c
c
c
( ) 0
T
H
p
c
=
c
i deal gases
0 =
T J

Throttlingd H=0)
( ) ( ) ( ) 0
p H T
H T H
T p p
c c c
+ =
c c c
( ) ( ) 0
p J T T
H H
T p

c c
+ =
c c
Structure of air-conditioner
Structure of
refrigerator
Operating principle of a refrigerator

Animation of refrigeration
Compression-type
refrigerating machine 01


Compression-type
refrigerating machine 02


Linde cycle for
liquefaction of gas

0201.swf
0202.swf
02.swf
James Prescott Joule 18181889
181812
24

1866

18721887

18891011
Lord Kelvin
18241907 19
W.
William Thomson
1824626
19071217

1866
1892

1846

53
1899
1904

Sir
William
Thomson
working on a
problem of
science in 1890
Summary
U=Q+W
2
1
V
ex
V
W p dV =
}
2
1
V
V
W pdV =
}
(reversible process)
0 0 2 2 1 1
1 1
2 1
1 1
1 1
p V p V pV
W
V V

| |

= =
|

\ .
(adiabatic reversible)
pV

=const (adiabatic reversible for ideal gas)

Heat
2
1
,
T
p p m
T
Q C dT =
}
2
1
T
,
T
V V m
Q nC dT =
}
p V
T p
U V
C C p
V T
( c c
| | | |
= +
| | (
c c
\ . \ .


p V
C C nR =
H U pV = +
2
1
T
,
T
p p m
H nC dT A =
}
2
1
T
,
T
V V m
U nC dT A =
}
Reaction heat
( )
r m B f m
B
H H B v A = A

! !
( )
r m B C m
B
H H B v A = A

2
1
2 1 ,
( ) ( )
T
r m r m r p m
T
H T H T C dT A = A + A
}
J T
H
T
p

| | c
=
|
c
\ .
Throttling expansion
Home work
Page 72
2.1 (basic concept)
2.2 (basic concept)
2.3 (calculation of work)
2.4 (calculations of work and heat)
2.9 (Calculate Q, W, U, and H )
2.12 (Calculation of Wr, Q, U, H of
phase change process)
2.20 (Calculation of adiabatic process)
2.25 (Calculation of the enthalpy of
formation)
2.24 (reaction heat)