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 sys
tem. 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, ρ, etc.
• any extensive variable divided by the moles or ma
ss becomes an intensive variable.
 2.1.3 State and state function

• State
• 状态是指系统的各种内在及外在性质在
一定条件下的宏观表现。 ( 化工 2004 一
同学）
• State function
• a property of a system that is not dependent
on the way in which the system gets to the s
tate in which it exhibits that property.
 Two properties of state functions
• (1) the infinitesimal changes of a state funct
ion can be expressed in total differential. e.g
. z=f(x,y)
 z   z 
dz    dx    dy
 x  y  y  x
• (2) Any changes between the initial and fina
l states depend only on the state of the syste
m not on the paths through which the chang
e takes place.
ΔT=T2 － T1 ， ΔU=U2 － U1
ΔY=Y2 － Y1 ， ΔX=X2 － X1

Y A
B
X
 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 t
o finial state.
• Path is the intermediate steps between the initial s
tate and the final state in a change of state.
• Isobaric: process done at constant pressure, p1=p2
=psur.
• Isochoric: process done at constant volume, V1=V2
.
• Isothermal: process done at constant temperature,
T1=T2=Tsur.
• Adiabatic: process where Q = 0, that is, no heat e
xchanges
• 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 tran
sferred in a driving force of temperature difference
.
• the zeroth law of thermodynamics
• If two bodies are in thermal equilibrium with a thir
d body, they are also in thermal equilibrium with e
ach 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 m
elts
• Solution A
• System ： You
• Surroundings ： Ice + the rest of the universe
• Q < 0 ： Heat flows out of the system (you) into th
e ice.
• Solution B
• System ： Ice
• Surroundings ： You + the rest of the universe
• Q > 0 ： Heat flows into the system (ice) from you.
• Example
• H2 burns in a heat insulated (adiabatic)
container filled with O2. what is the heat
sign of this process? Positive, negative, or
zero?
 Work
• Work (W): All the transferring form of ener
gy except heat.
• There are several kinds of work. Pressure-v
olume (pV) work, electrical work, surface w
ork, and mechanical work, etc.
• non-volume work (W’): Except pressure-v
olume work, all the other works.
 Work sign

W>0
系统 环境
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, the
y can not be expressed in total differential. The inf
initesimal changes are denote by δQ and δW instea
d of dQ and dW, respectively. Their magnitudes de
pend on the path
 Computation of pV work

V2 V2
 W   pex dV W   W   
V1
V1
pex dV
 V2
W    pex dV
V1
 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
V2
W    pdV (reversible pex =p  dp)
V1

• For ideal gas

V2 nRT
W   dV (ideal gas)
V1 V
V1
dV V
W  nRT   nRT ln 2 (T  constant)
V2
V V1

V2
W  nRT ln (ideal gas, reversible expansion,T  const)
V1
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 dm3 to a final
volume of 40 dm3.
• Solution

V2 40
W   RT ln   RT ln  1728 J
V1 20
 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 100°C,
respectively.
• Fahrenheit scale
• The corresponding values on the Fahrenheit
scale are 32°F and 212°F
• 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-def
ined zero on this scale. p→0 ， T→0.
• 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 i
dentical to Kelvin temperature scale based on Carnot h
eat 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=1m
ol kg-1, standard pressure p =100 kPa or standar
d concentration c = 1mol dm-3 and exhibiting inf
initely dilute solution behavior.
• Solvent in solution or component in liquid mixt
ure
• Standard state: Pure liquid at 100kPa
• The standard state of a system can be defined at an
y given temperature.
• a few texts (especially in related disciplines such a
s physics and engineering) use 0 degrees Celsius f
or Standard Temperature and Pressure (STP).
 2.2 The first law of
thermodynamics
• 2.2.1 The first law of thermodynamics
dU   Q   W
U  Q  W
• 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.
 2.2.2 Heat and enthalpy
• Heat depends on the path in which a process t
akes place.
• QV symbolizes the heat at constant volume.
• Qp symbolizes the heat at constant pressure.
• If we assume that W’=0, then at constant volu
me δW = － pdV =0.
• Qv = △U - W
• Qv = △U=U2-U1
 Heat at constant pressure
• If we assume that W’=0, then at constant pressure
•  Qp = △U - W
• Qp = △U + p△V    (p1 = p2 = pex)
• Qp = U2 - U1 + p (V2 -V1)
•  Qp = U2- U1 + pV2 - pV1
• Qp = U2+ pV2 - U1 - pV1
• Qp = (U2 + pV2) - (U1+ pV1) 
• 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
• △U ＝ Q ＋ W ＝ 0
 U   U 
dU    dV    dT  0
 V T  T V
 U 
• Since dT = 0, dV  0 it follows that   0
 V T

• For ideal gases at constant temperature

H  U  pV  U  nRT

• H=f(T)
 2.2.4 Molar heat capacity
heat capacity: C(T)= δQ/dT

1 Q
Cm (T ) 
n dT

CV (T ) 1 QV 1 dU T2
CV ,m 
n
 
n dT n dT
QV  U   T1
nCV , m (T ) dT

C (T ) 1 Q p 1 dH T2
C p ,m (T )  p   Q p  H  
T1
nC P , m (T ) dT
n n dT n dT
• For ideal gases

T2

 p H   nC p ,m dT
T2
U   nCV ,m (T )dT
T1
T1

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 CV and Cp
 H   U     U  pV    U 
C p  CV         
 T p  T V  T p  T V
 U   V   U 
   p    
 T  p  T  p  T V
 U   U 
from U  （ f T，V）, dU    dT    dV
 T V  V T
at cons t ant p, di f f er ent i at e t hi s equat i on and obt ai n：
 U   U   U   V 
       
 T  p  T V  V T  T  p
 U 
Substitute   into the first euqation
 T  p
 U    V 
CP  CV     p  
 V T  T p
  U    V 
CP  CV     p  
 V T   T  p

The first term indicates the increase of U, and the

second volume work.
For ideal gas
 U   V    ( pV )    (nRT ) 
   0; p       nR
 V T  T  p  T  p  T  p
C p  CV  nR; or C p ,m  CV ,m  R

For condensed phase

 V 
   0; C p  CV
 T  p
 Heat capacities of ideal gases
• Equipartition of Energy Theorem states that mo
lecules in thermal equilibrium have the same avera
ge energy associated with each independent degre
e of freedom of their motion and that the energy is
(1/2)RT per mole.
• For a monoatomic ideal gas
CV ,m  32 R C p ,m  52 R
•For a diatomic ideal gas
CV ,m  52 R C p ,m  72 R
2.2.4.4 Temperature dependent
of molar heat capacity
By suming up huge number of experiments, Cp,m ＝ f(T)
is ordinary expressed as ：
Cp ， m= a + b T + c T2
Cp ， m= a + b T + c’T － 2
Cp ， m= a + b T + c T2 + d T 3
a ， b ， c ， d ， c’ are all constats which can
be found in appendix D in our textbook.
Pay special attention on the valid temperature ra
gne for the calculation of Cp by using these constants
.
  a  bT  cT  dT
T2
Qp  n 2
T1

b 2 c 3
 na  T2  T1   n  T2  T1   n  T2  T13 
2

2 3

average molar heat capacity at constant pressure:

T2

C p ,m 
Qp


T1
C p ,m dT
T2  T1 T2  T1
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 ：

CV  y ACV ,m , A  y B CV ,m , B

C p  y AC p , m , A  y B C p , m , B

y is mole frction of compents of gaseous mixture.

 2.2.5 Reversible adiabatic process of
an ideal gas
• From the first law: dU = δQ + δW
• For the reversible adiabatic process δQ = 0.
dU   W   pdV
• for ideal gases
dU  nCV ,m dT p  nRT / V
dT R dV
nCV ,m dT  (nRT / V )dV T

CV , m V
R C p ,m  CV ,m C p,m
    1 where  =
CV ,m CV ,m CV , m

• γ is called ratio of heat capacity or adiabatic ind

ex.
 dT dV T2 V2
 (  1) ln  -( -1) ln
T V T1 V1
 1
T2  V1 
 
T1  V2 

• Using the ideal gas law to replace V, we get

the other two equations
 1
T2  p2  
 
 
T1  p1 
p V  p2V2
1 1


pV  constant.
• The work done on or take by system is
V2 V2
W    pdV   p V 

0 0 V dV / V 
V1 1

p0V0
where p  
V
• Integrating this leads to
p0V0  1 1 
W   1   1 
  1  V2 V1 

• p0, V0 are pressure and volume of system at

any state.
 The above equation can be changed into a
simple form

pV 

1 1  1  p2V2
p1V1 

W 0 0
  1   1     1   1 
  1  V2 V1    1  V2 V1 
p2V2  p1V1
W
 1
 W 定温 > W 绝热
p A (p1,V1)

等温线

B (p2,V2)
绝热线

C (p3,V2)

V
V1 V2
Comparision of isotherms to adiatats
 Example
1mol 双原子理想气体从 25℃ ， 100kPa 突然绝热恒外
压减压至 50kPa ，求终态温度 T2 及 W 、△ U 、△ H 。
解：因为绝热， Q=0 ， △ U=W=-pamb△V
nCV,m(T2-T1)= -p2(V2-V1)
V2=nRT2/p2 ； V1=nRT1/p1 代入上式，解出 T2=255.56K

△U=nCV,m△T=(5/2)R(255.56-298.15)=-885.3 J
△H=nCp,m△T= (7/2)R(255.56-298.15)=-1239 J

△H= △U+△(pV)=△U+R△T
=-885.3+8.3145(255.56-298.15)=-1239 J
 Example: 4 mol 双原子理想气体从 p1=50kPa, V1=160dm3 绝
热可逆压缩至 p2=200kPa 。求末态温度 T2 及 W ，△ U ，△ H
。
解：先求 T1=p1V1/nR=240.53K
C p ,m CV ,m

 1 CV ,m CV ,m C p ,m CV ,m R
T2  p2    p2  C p ,m
 p2  C p ,m  p 2  C p ,m
    CV ,m    
T1  p1   p1   p1   p1 

T2=(p2/p1)R/Cp,mT1=357.43K
△U=nCv,m(T2-T1)=9.720kJ
△H=nCp,m(T2-T1)
W=△U
 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 H m ,  fus H m ,  sub H m , trs H m
 Phase change at constant pressure
Q p  H 
 H  H (  )  H ( )


The molar change of

enthalpy
 
 H m   H / n
For melting and crystal transition process at constant
pressure and constant temperature
Qp  H 　　　W   pV  0　　　　U  H
• For vaporization and sublimation processes
Q p  H
W   pV   pV ( g )  nRT
U  H   ( pV )  H  pV ( g )  H  nRT
 example

100℃ ， 50dm3 真空容器内有一小瓶，瓶内有

50g 水。将小瓶打破，蒸发到平衡，求 Q ， W ，
△ U ，△ H 。已知水的△ vapHm=40.668kJ mol-1 。
解：水只能部分蒸发。设为 n mol 。
n=pV/RT=1.633mol, 即 29.42g 。
△H=1.633×40.668=66.41kJ
W=0
Q=△U=△H-△(pV)=△H-pV(g)
=△H-nRT=61.34kJ
Temperature dependence of enthalpy
of phase change
 H (T2 )  H m ( )   H (T1 )  H m (  )
T1

H m ( )   C p,m ( )dT
T2
T2

H m (  )   C p,m (  )dT
T1

Cp,m =C p ,m (  )-C p ,m ( )
T2

H m ( )+H m (  )   C p ,m dT
T1
T2

 H m (T2 )   H m (T1 )+  C p ,m dT

T1
 2.4 Standard molar enthalpy of
reaction
2.4.1 Stoichiometric coefficients
　 aA + bB = yY + zZ
　 0= － aA － bB ＋ yY+zZ

0  B B

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
dξ=dnB/υB
for a same reaction, if the equation of che
mical reaction is written in different form, νB
will also be different, and then extent of reacti
on ξ will be different too.
For example:
N2(g)+3H2(g)= 2NH3(g)
½ N2(g)+ 3/2 H2(g)= NH3(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 H   nY H m* (Y )  nZ H m* ( Z )    n A H m* ( A)  nB H m* ( B ) 

 r H m   r H /    B H m* ( B )
B

△rHm is molar enthalpy of reaction; * stands for a pure substa

nce.
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.
T , p! T , p! T , p! T , p!
 r H m!
 A A   B B 
  LL  M M
pure pure pure pure

 r H my   B H my ( B )
B
 2.5 Calculation of standard enthalpy of reactions

2.5.1 Standard molar enthalpy of formation

Standard molar enthalpy of formation  f H my
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  f H m!  0
For example:
C(graphite) + O 2 (g) = CO 2 (g)  f H m! (CO 2 , g)  393.509 kJ mol -1
H 2 (g) + S(正交rhombic) = 2O 2 (g) + H 2SO 4 (l)
2Hg(l) + Cl 2 (g) = Hg 2 Cl 2 (s)
 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

p !
p !
p !
p ! H1   A  f H m! (A)  B  f H m! (B)
 r H m!
- A A + - B B    YY +  ZZ H 2   Y  f H m! (Y)  Z  f H m! (Z)
pure pure pure pure
H1   r H m!  H 2

¦ ¤ H2
¦ ¤ H1
 r H m!  H 2  H1
The same stable   Y  f H m! (Y)   Z  f H m! (Z)   A  f H m! (A)   A  f H m! (B)
elements in the
same quantities at
 r H m!   B  f H m! ( B)
standard pressure

B
 Example Calculate the standard enthalpy of following reaction
at 25℃ by using standard molar enthalpy of formation

2C 2 H 5OH(g)  C4 H 6 (g)  2H 2O(g)  H 2 (g)

Solution
C2H5OH(g) C4H6(g) H2O(g) H2(g)
f H y
m

kJ  mol 1 -235.10 110.16 -241.81 0

 r H my   f H my (C4 H 6 , g)+2 f H my (H 2 O, g)
 2 f H my (C 2 H 5OH, g)
= [110.16  2  241.818  ( 2  235.10)]kJ  mol 1
 96.72kJ  mol 1
note  f H m (H 2 O, g, T )   f H m (H 2O, l, T )   vap H m (H 2 O, T )
y y y
 2.5.2 Standard molar enthalpy of combustion
Definition: The enthalpy change when a mole of substance is com
pletely burnt in oxygen at a given temperature and standard pressure.
 H
The general
$
m ( B, T )
c convention for the products of combustion is as follo
ws. Carbon in organic compound becomes CO2(g); H becomes H2O(l);
N becomes N2(g); S becomes SO2(g); Cl becomes HCl(aq) and so on.
All these complete products have an enthalpy of combustion of ze
ro.

For example, under 298.15K and standard pressure:

CH 3COOH(l)  2O 2 (g)  2CO 2 (g)  2H 2O(l)
 r H m$  870.3 kJ  mol-1
 c H m$ (CH3COOH,l,298.15 K)  -870.3 kJ  mol -1
 用图解的方法表示燃烧热与反应热的关系

△H1 △H2

反应物和产物均为相同的氧化产物

△H1= △Hm+ △H2 即 △ Hm= -(△H2 - △H1)

 r H m$ (298.15 K)  - B  c H m$ (B,298.15 K)

B
For example

(COOH) 2 (s)  2CH 3OH(l)  (COOCH 3 ) 2 (s)  2H 2O(l)

A B C D

 r H m$   c H m$ (A)  2c H m$ (B) - c H m$ (C)

Determination of heat of combustion
 2.5.3 Dependence of standard molar enthalpy of reaction
on temperature
 r H m (T1 )
aA + bB yY + zZ
 H1 H 2 H 3  H 4
 r H m (T2 )
aA + bB yY + zZ

 r H my  T1   H1y  H 2y   r H my  T2   H 3y  H 4y
T2 T2
since  H  a  C p,m (A)d T,  H  b  C p,m (B)d T,

1
 
2

T1 T1
T2 T2
H y

3

C p,m (Y)d T,  H   z 

4

C p,m (Z)d T,
T1 T1

T2
then  r H (T2 )   r H (T1 )    B C p ,m ( B)dT
y
m
y
m T 1

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 W≈0, and Δ(pV)≈0, then for s
olids and liquids Q≈ΔH≈ΔU.
• reactions involving gases
• the product pV may be replaced by νBRT
 r H m   rU m  RT  B ( g ) Q p  QV  RT  B ( g )
B B

when 
B
B ( g )  0, then  r H m   rU m , or Q p  QV

• when 
B
B ( g )  0, then  r H m   rU m , or Q p  QV
 2.5.5 Hess’s Law and reaction enthalpy

• Hess’s 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) + 2H2(g) → CH4(g)
• Consider following reactions
CH 4 (g) + 2O 2 (g)  CO 2 (g) + 2H 2O(l)  r H my ,a  890.35kJ  mol-1 (a)
H 2 (g) + 12 O 2 (g)  H 2O(l)  r H my ,b  285.84kJ  mol-1 (b)
C(graphite) + O 2 (g)  CO 2 (g)  r H my ,c  393.51kJ  mol-1 (c)

• The combination of these three reactions fro

m –(a)+2(b)+(c), we get the above studied r
eaction.
• Then
r H   r H
y
m
y
m ,a  2 r H y
m ,b  r H y
m ,c

 r H my  －(－890.35)  2  (－285.84)  (－393.51)

-1
 －74.84kJ  mol
 2.5.6 The maximum temperatures of
flames and explosions
• The temperature reached for a combustion r
eaction at constant pressure and adiabatic sy
stem is known as the maximum temperatu
re of flame. Qp=ΔH=0
• the temperature reached for an explosion in
an adiabatic system and at constant volume
is called the maximum temperature of exp
losion. QV=ΔU=0
 例 甲烷 (CH4, g) 与理论量二倍的空气混合，始态温度 25
℃ ，在常压 (p≈100kPa) 下燃烧，求燃烧产物所能达到的最高温
度。设空气中氧气的摩尔分数为 0.21 ，其余为氮气，所需数据
查附录。

解：甲烷 (CH4,g) 的燃烧反应为

CH4(g)+2O2(g) ＝ CO2(g)+2H2O(g)
先求反应的 rHm ，可以用各反应组分的 fHm 来计算 rH
m ，我们这里用 cH m(CH4,g) 来计算 rH m
 
 rHm
CH4(g)+2O2(g) CO2(g)+2H2O(g)

cHm(CH4,g) △vapHm(H2O)
CO2(g)+2H2O(l)

rHm = cHm(CH4,g)+ vapHm(H2O)

= － 802.286kJ
 对于含 1mol 甲烷 (CH4,g) 的系统，含氧气 4
mol ，氮气（ 4/0.21 ） ×0.79mol=15.05mol
，则
始态 T0=298.15K T
Qp=H=0 CO2(g)1mol, H2O (g) 2mol
CH4(g)1mol,O2 (g) 4mol
N2 (g) 15.05mol O2 (g) 2mol,N2 (g) 15.05mol
恒压绝热

rHm H2
T0=298.15K
CO2(g)1mol, H2O (g) 2mol
O2 (g) 2mol,N2 (g) 15.05mol

Qp= H = rHm + H2 =0

H 2   C p ,m  CO 2 , g   2C p ,m  H 2 O, g   2C p ,m  O 2 , g   15.05C p ,m  N 2 , g dT
T

T0

将附录中的 CO2(g) , H2O(g) ,O2(g) ,N2 (g) 的

定压摩尔热容 Cp,m= a+bT+cT2 代入上式 。
再代入方程 rHm+ H2= 0 ，解 T ，得
T =1477K
即最高火焰温度就是恒压绝热反应所能达到的最高
温度。
而最高爆炸温度就是恒容绝热反应所能达到的最高
温度。
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

thermometer Adiabatic wall

p1,V1,T1 p2,V2,T2

Porous plug

throttle expansion ， p1 ＞ p2
 点击图像可以
看动画
 节流过程是在绝热筒中进行的， Q=0 ，所以：
U 2  U1  U  W
开始，环境将一定量气体压缩时所作功
（即以气体为系统得到的功）为：
W1   p1V  p1V1 (V =0 V1  V1)
气体通过小孔膨胀，对环境作功为：

W2   p2V   p2V2 (V =V2  0  V2 )

 在压缩和膨胀时系统净功的变化应该是两
个功的代数和。
W  W1  W2  p1V1  p2V2

即 U 2  U1  p1V1  p2V2

移项 U 2  p2V2  U1  p1V1

H 2  H1
节流膨胀过程是个等焓过程。 H = 0
 2. 节流膨胀的热力学特征及焦 - 汤系数
T
 J-T  ( )H
p

称为焦 - 汤系数（ Joule-Thomson coefficient), 它表示经节流过

程后，气体温度随压力的变化率。

 J -T >0 经节流膨胀后，气体温度降低。
 J -T <0 经节流膨胀后，气体温度升高。
 J -T =0 经节流膨胀后，气体温度不变。
 Show that for ideal gases  J T  0
H= f ( T, p)
H H
dH  ( ) p dT  ( )T dp  0 Throttling ： d H=0)
T p
H T H
( )p( )H  ( )T  0
T p p
H H
( ) p   J T  ( )T  0
T p
H H
( )T ( )T
T p p
 J T  ( )H   
p H Cp
( )P
T
H
i deal gas es (
p
)T  0
  J T  0
Structure of air-conditioner
Structure of r
efrigerator
Operating principle of a refrigerator
 Animation of refrigeration
• Compression-type refriger
ating machine 01 02ѹËõʽÖÆÀä01.swf

• Compression-type refriger
ating machine 02 02ÕôÆûѹËõʽÖÆÀä02.swf

• Linde cycle for liquefactio

n of gas 02´øÔ¤ÀäµÄ½ÚÁ÷Ñ­» ·.swf
James Prescott Joule 1818 ～ 1889
焦耳是英国物理学家。 1818 年 12
月 24 日生于索尔福。他父亲是酿
酒厂的厂主。焦耳从小体弱不能上
学，在家跟父亲学酿酒，并利用空
闲时间自学化学、物理。他很喜欢
电学和磁学，对实验特别感兴趣。
后来成为英国曼彻斯特的一位酿酒
师和业余科学家。焦耳可以说是一
位靠自学成才的杰出的科学家。
焦耳最早的工作是电学和磁学方面
的研究，后转向对功热转化的实验
研究。
1866 年由于他在热学、电学和热力
学方面的贡献，被授予英国皇家学
会柯普莱金质奖章。
1872 年— 1887 年焦耳任英国科学
促进协会主席。
1889 年 10 月 11 日焦耳在塞拉逝世
。
 开尔文（ Lord Kelvin
1824 ～ 1907 ） 19 世纪英国
卓越的物理学家。原名 W. 汤
姆孙（ William Thomson ），
1824 年 6 月 26 日生于爱尔兰
的贝尔法斯特， 1907 年 12
月 17 日在苏格兰的内瑟霍尔
逝世。由于装设大西洋海底
电缆有功，英国政府于 1866
年封他为爵士，后又于 1892
年封他为男爵，称为开尔文
男爵，以后他就改名为开尔
文。
1846 年开尔文被选为
格拉斯哥大学自然哲学教授
，自然哲学在当时是物理学
的别名。开尔文担任教授 53
年之久，到 1899 年才退休。
1904 年他出任格拉斯哥大学
校长，直到逝世。
 Sir
William
Thomson
working on a
problem of
science in 1890
 Summary
• △U=Q+W

V2
W    pex dV
V1

V2
W    pdV (reversible process)
V1

p0V0  1 1  p2V2  p1V1

W   1   1   (adiabatic reversible)
  1  V2 V1   1

pVγ=const (adiabatic reversible for ideal gas)

 Heat
T2
T2
Q p   C p ,m dT QV   nCV ,m dT
T1 T1

  U    V 
C p  CV   p      理想 C p  CV  nR
  V T   T p
气体： T 2

H  U  pV  p H   nC p , m dT
T1

T2

V U   nCV ,m dT
T1
 Reaction heat

 r H m!   B  f H m! ( B )   B  C H my ( B )
 r H my 　
B B

T2

 r H my (T2 )   r H my (T1 )    r C yp ,m dT
T1

 T 
Throttling expansion ：  J T  
 p  H
 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, ΔU, and ΔH )
• 2.12 (Calculation of Wr, Q, ΔU, ΔH of phas
e change process)
• 2.20 (Calculation of adiabatic process)
• 2.25 (Calculation of the enthalpy of
formation)
• 2.24 (reaction heat)