Thermodynamics

1. Introduction
2. Temperature and Heat
3. The Idea Gas Law and Kinetic Theory
4. The first law of thermodynamics
4.1. Thermodynamic processes
4.2. Internal energy, heat and work
4.3. The first law of thermodynamics
4.4. A closer look at heat and work
5. Application of 1st law to ideal gas
5.1. Isochoric process (constant volume)
5.2. Isobaric process (constant pressure)
5.3. Isothermal process (constant temperature)
5.4 Adiabatic process (without heat exchange)
6. Carnot cycle
7. The second law of thermodynamics
1 8. Statistical view of 2nd law and entropy
 4. The first law of thermodynamics
Energy conservation

2
 4.1. Thermodynamic processes
4.1.1 Thermodynamic processes

1( p1 , V1 , T1 ) → → 2( p 2 , V 2 , T2 )

4.1.2 Quasi-static processes

1( p1 , V1 , T1 ) → ( p i , V i , Ti ) → 2( p 2 , V 2 , T2 )
1 2

3
 1.3 p ~ V （ T ~ V 、 p ~ T ） P lot
A point：an equilibrium state
A curve：a quasi-static process

p
1(p1,V1,T)

2(p2,V2,T)

V
O
4
 4.2. Internal energy, heat and work
4.2.1 Internal energy

Real gas:

E = f (V , T )

Ideal gas:
Internal energy depends only on temperature.

i
E = f (T ) ⎯⎯ ⎯ ⎯ ⎯ ⎯ ⎯→ nRT
Energy equipartition

2
➢ Microscopic energy contained in a substance, given by the random,
disordered kinetic energy of the molecules
5
 4.2.2 Two approaches to change the internal energy

Doing Work

F
p

6
 Transfer Heat

7
 Heat equivalent of work:

• The temperature of a body

can be increased by doing
work on it.
• Heat and work are the two
distinct methods of energy
transfer.
• Heat is energy transferred
solely due to a temperature
difference.

James Joule's famous experiment which demonstrated

8 the mechanical equivalence of heat
 4.3. The first law of thermodynamics
The internal energy Eint of a system tends to increase if energy is
added as heat Q and tends to decrease if energy is lost as work W
done by the system.

E = Q − W
Infinitesimal process:

dE = dQ − dW
Q A
p1 p2
E1 E2
9
10
 4.4. A closer look at heat and work
4.4.1 Work done in quasi-
static process F
p
dW = pSdl = pdV
V2 p dl
W =  pdV 1
V1
n

m
➢ W ork done depends on the path: 2
Wm  Wn
11 O V1 V2 V
 4.4.2 Heat in the quasi-static process and heat capacity

p
Heat:
1
Q = E + W n

m
dQ = dE + dW 2

O V1 V2 V

12
 Absorption of heat

Heat capacity dQ
How much heat is needed to raise one degree in
C=
temperature for the matter
dT

Specific heat
How much heat is needed to raise on degree in
c = C /m
temperature for one kg of matter

Molar specific heat Cm = C / n = Mc

How much heat is needed to raise on degree in
temperature for one mole of matter

➢ C、c and Cm depend on individual process

13
 dQ
C= →
dT

T2 T2 T2
Q= T1
CdT = m  cdT = n  C m dT
T1 T1

C 、 c、 C m＝ co n st. →

Q = C (T 2－ T1 )= m c (T 2－ T1 )= n C m (T 2－ T1 )

14
 Heat
Recall heat required for temperature change

Q = C (T 2－ T1 )= m c (T 2－ T1 )= n C m (T 2－ T1 )
Heat transfer in a phase change

Lf heat of fusion (or sometimes latent heat of fusion)

Lv heat of vaporization

15
 5. Application of 1st law to ideal gas

16
 5.1. Isochoric process (constant volume)
i
E = nR(T2 − T1 )
2
W =0
i
Q = E = nR(T2 − T1 )
2
i
CV ,m = R p
2 2(p2, V1, T2)

Q
V＝const.
1(p1, V1, T1)
O V
17 (p1/T1=p2/T2)
 5.2. Isobaric process (constant pressure)
i
E = nR (T2 − T1 )
2
V2
W =  pdV = p (V2 − V1 ) = nR (T2 − T1 )
V1

i+2
Q = E + W = nR (T2 − T1 )
2
i+2
C p ,m = R p
2

W 1(p1, V1, T1) 2(p1, V2, T2)

Q
p＝const.

O V
18 (V1/T1=V2/T2)
 5.3. Isothermal process (constant temperature)
E = 0
V2 V2nRT V2
W =  pdV =  ( ) dV = nRT ln
V1 V1 V V1
V2 p1
Q = W = nRT ln = nRT ln
V1 p2
CT , m =  p
1(p1, V1, T1)
W
Q
T＝const.
2(p2, V2, T1)

O V
19 (p1V1=p2V2)
 5.4. Adiabatic process (without heat exchange)
Greek: adiábatos, "impassable"
• An adiabatic process is a type of thermodynamic process
in which there is no heat and mass transfer between the
system and its surroundings that is no amount heat or mass
can exit or enter the system
• Fast pace process, good thermal insulator

W
Q＝0

20
 Adiabatic equation W
Q＝0
dQ = dE + pdV 
  pdV = − nCV , m dT .......(1)
dQ = 0 dE = nCV , m dT 
1
pV = nRT  dT = ( pdV + Vdp ) .......(2)
nR
CV , m + R dV P
dp dV
=− = −
p CV , m V V

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➢Isothermal and Adiabatic curve

 dp pA
 Isothermal ( dV )T = − V
 A

 Adiabatic : ( dp ) = − p A
 dV
S
VA
dp dp
( ) S  ( )T
dV dV

22
 E、W、Q for adiabatic processes

i
E = nR (T2 − T1 )
2
Q=0
i
W = −E = − nR (T2 − T1 )
2
p
1(p1, V1, T1)
 p1V1 = p2V2
  −1  −1
 1 1
T V = T V
2 2
  −1 −   −1 − 
 p1 T1 = p2 T2
2(p2, V2, T2)
23 O V
 V2
Solution 2： According to W =  pdV :
V1

V2 V2p1V1
W =  pdV =  (  )dV
V1 V1 V
p1V1 1 1
= (  −1 −  −1 )
 − 1 V1 V2
p1V1 − p2V2
=
 −1

24
25
 Ex. 11-1 A system of 0.014kg N2 gas in the standard state
undergoes the
(1) isobaric process;
(2) isothermal process;
(3) adiabatic process,
respectively. The volume of gas is then expanded twice.
Compute E , W and Q for the above three processes,
respectively.

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Solutioin：
T1 T2 V2
（1） = → T2 = ( )T1 = 546 K
V! V2 V1
5
E = nR (T2 − T1 ) = 2.86 103 ( J )
2
W = p1 (V2 − V1 ) = p1V1 = nRT1 = 1.13  103 ( J )
Q = W +  E = 3.99  10 ( J )
3

（2） E = 0
V2
W = nRT1 ln = 7.86 10 2 ( J )
V1
Q = W +  E = 7.86  10 2 ( J )
27
  −1  −1 V 2  −1
（3） T V
1 1 = T 2V 2 → T2 = ( ) T1 = 206.9 K
V1
5
E = nR (T2 − T1 ) = −6.87  10 2 ( J )
2
W = −E = −6.87  10 ( J )
2

Q=0

28
 Ex. 11-2 Calculate the change of internal energy,
work done and heat transfer of the system for the
process shown by the line in the figure below. (The
system of DOF i=5)
p(105Pa)

a
6

2 b

O 1 2 V(10－3m3)
29
Solution:
5 5
E = nR(Tb − Ta ) = ( pbVb − paVa ) = −500( J )
2 2

Vb 1
W =  pdV = ( pa + pb )(Vb − Va ) = 400( J )
Va 2
Q = E + W = −100( J )

30
Ex. 11-3 For a system of 1 mol monatomic ideal gas, its volume is
first expanded twice via an isobaric process from the initial state a
( p1, V1). And the system is then heated as to increase its pressure
twice by keeping the volume constant. The system is finally
expanded adiabatically until its temperature dropped to the initial
temperature. Calculate:
(1) the volume Vd for state d;
(2) the work done in the whole process; p
(3) heat absorbed in the whole process.
2p1 c

p1 a b

d
o V
31 V1 2V1
 p
Solution:
(1) c
Ta = Td 2p1
p1V1
Td = Ta =
R p1 a b
Tb = 2T a Tc = 4T a d
According to adiabatic equation o V
V1 2V1
 −1  −1
T cV c = TdV d
1
Tc  −1
Vd = ( ) Vc = 16V1
Td
32
 p
(2)
2p1 c
W a b = p 1 ( 2 V 1 − V 1 ) = p 1V 1
W bc = 0 p1 a b

W cd = −  E cd = C V ( T c − T d ) d
o V
V1 2V1
3 9 9
= R ( 4T a − T a ) = RT a = p1V1
2 2 2
11
W = W ab + W bc + W cd = p1V1
2
33
 （3）Two approaches to calculate the heat transfer

Approach 1： p

2p1 c

Qab = C P (Tb − Ta )
p1 a b
5
= R (Tb − Ta )
2 d
5 5 o V
V1 2V1
= ( pbVb − paVa ) = p1V1
2 2

34
 Qbc = CV (Tc − Tb ) p
3
= R (Tc − Tb ) c
2 2p1
3
= ( pcVc − pbVb ) = 3 p1V1
2 p1 a b
Q cd = 0
d
11
Then Q abcd = p1V1 o
V1 2V1
V
2

35
 Approach 2：

Q a b cd = W a b cd +  E cd p
c
Ta = Td   E ad = 0 2P1
11
Thus Q abcd = W abcd = p1V1 P1 a b
2
d
o V
V1 2V1

36
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