Thermodynamics

Isothermal process on p-V, T-V, and p-T diagrams
isothermal T = T0 = constant
a = (p1, V1, T0)
b = (p2, V2, T0)
pV = nRT0
p
p1
a
T0
p2
W
V1
T0
nRT0
p(V) =
V
PHYS 1101, Winter 2009, Prof. Clarke
p2
b
V2
p1
V1
V2
T(V) = T0
T0
p(T) = multivalued
1
Isochoric process on p-V, T-V, and p-T diagrams

isochoric V = V0 = constant
a = (p1, V0, T1)
b = (p2, V0, T2)
pV0 = nRT
p
p1
T1
p1
p2
T2
p2
V0
p(V) = multivalued
V0
T(V) = multivalued
b
T2
T1
nRT
p(T) =
V0
2
Isobaric process on p-V, T-V, and p-T diagrams

isobaric p = p0 = constant
a = (p0, V1, T1)
b = (p0, V2, T2)
p0V = nRT
p
p0
T2
p0
W
V1
T1
V2
p(V) = p0
T1
T2
a
V1
V2
p0V
T(V) =
nR
p(T) = p0
3
Clicker question 1
Consider the p-V diagram below in which the system evolves from a b
c. If T0 ~ 240K (and thus RT0 = 2,000 J mol1), how many moles of
gas, n, are in the system?
a) 5
p (Nm2)
105
isobar
b
isotherm
T0
isochor
pc
1
b)
c)
d)
e)
105
50
1,000
Not enough information to tell
Vc V (m3)
first law of thermodynamics: Eint = Q W ( = nCVT )

ideal gas law: pV = nRT
Clicker question 1
c. If T0 ~ 240K (and thus RT0 = 2,000 J mol1), how many moles of
gas, n, are in the system?
a) 5
p (Nm2)
105
isobar
b
isotherm
T0
isochor
pc
1
Vc V (m3)
b)
c)
d)
e)
105
50
1,000
pV
100,000
n =
=
= 50
RT0
2,000

Clicker question 2
c. What is Vc, the volume at state c?
p
a) 0.5 m3
(Nm2)
105
b
T0
c
pc
1
b)
c)
d)
e)
2.0 m3
4.0 m3
8.0 m3
Vc V (m3)

Clicker question 2
p
a) 0.5 m3
(Nm2)
105
b
T0
c
pc
1
Vc V (m3)
b)
c)
d)
e)
2.0 m3
4.0 m3
8.0 m3
need to know pc

Clicker question 3
p
a) 0.5 m3
(Nm2)
105
b
T0
c
5 104
1
b)
c)
d)
e)
2.0 m3
4.0 m3
8.0 m3
Vc V (m3)

Clicker question 3
p
a) 0.5 m3
(Nm2)
105
b
T0
c
5 104
1
Vc V (m3)
b)
c)
d)
e)
2.0 m3
4.0 m3
8.0 m3
pa
pcVc = paVa Vc = p Va = 2 m3
c

Clicker question 4
c. What is the net change in internal energy, Eint?
a) 0 J
p (Nm2)
105
b)
c)
d)
e)
b
T0
c
5 104
1
5.0 104 J
about 7.0 104 J
105 J
V (m3)

10
Clicker question 4
c. What is the net change in internal energy, Eint?
a) 0 J
p (Nm2)
105
b)
c)
d)
e)
b
T0
c
5 104
1
(m3)
5.0 104 J
about 7.0 104 J
105 J
Eint = nCVT

11
Clicker question 5
c. What is the net work done by the system on its environment, W?
a) 0 J
p (Nm2)
105
b)
c)
d)
e)
b
T0
c
5 104
1
5.0 104 J
about 7.0 104 J
105 J
V (m3)

12
Clicker question 5
c. What is the net work done by the system on its environment, W?
a) 0 J
p (Nm2)
105
b)
c)
d)
e)
b
T0
c
5 104
1
5.0 104 J
about 7.0 104 J
105 J
V (m3)

13
Clicker question 6
c. What is the net heat transferred into the system, Q?
p
a) 5.0 104 J
(Nm2)
105
b)
c)
d)
e)
b
T0
c
5 104
1
5.0 104 J
105 J
105 J
V (m3)

14
Clicker question 6
c. What is the net heat transferred into the system, Q?
p
a) 5.0 104 J
(Nm2)
105
b)
c)
d)
e)
b
T0
c
5 104
1
V (m3)
5.0 104 J
105 J
105 J
Q = Eint + W = 0 + 105 J

15
Internal Energy (revisited)

f
f
nRT = NkT
Cp = CV + R
2
2
n = number of moles; 1 mole = 6.0221 1022 particles (NA)
N = number of particles
R = gas constant = 8.3147 J mol1 K1
k = Boltzmanns constant = 1.3807 1023 J K1
Eint = nCVT =
type of gas
degrees of specific heat at internal specific heat at

freedom
constant
energy
constant
(f)
volume (CV )
(Eint) pressure (Cp )
monatomic
diatomic
polyatomic (3)
~6
3
R
2
5
R
2
3
nRT
2
5
nRT
2
5
R
2
7
R
2
3R
3 nRT
4R
(Cp/CV )
5
3
7
5
4
3
16
Adiabatic processes
reversible
irreversible
a = (p1, V1, T1)

b = (p2, V2, T2)
a = (p1, V1, T0)

b = (p2, V2, T0)
pV = constant
p1V1 = p2V2
p
p
a
p1
adiabat
p2
V1
isotherms
T1
T2
p1
V2
T0
b
p2
V
isotherm
V1
V2
V
17
Clicker question 7
Consider the p-V diagram below in which the system evolves reversibly
along the adiabat from state a to state b. This gas is
p
a) monatomic ( = 5/3)
(kNm2)
b) diatomic ( = 7/5)
c) polyatomic ( = 4/3)
d) not enough information to tell
16
adiabat
1
1
8 V (m3)
pV = constant
18
Clicker question 7
along the adiabat from state a to state b. This gas is
p
a) monatomic ( = 5/3)
(kNm2)
b) diatomic ( = 7/5)
c) polyatomic ( = 4/3)
16
adiabat

8 V (m3)
pV = constant

paVa = 1(8) = 23 =

pbVb = 16(1) = 24
= 4/3 polyatomic
19
Clicker question 8
along the adiabat from state a to state b. How much heat is transferred to
the system?
a) 0 J
p (kNm2)
b)
c)
d)
e)
16
adiabat
8 kJ
16 kJ
128 kJ
not enough information to tell
1
1
8 V (m3)
pV = constant
20
Clicker question 8
along the adiabat from state a to state b. How much heat, Q, is
transferred to the system?
a) 0 J
p (kNm2)
b)
c)
d)
e)
16
adiabat
1
1
8 V (m3)
8 kJ
16 kJ
128 kJ
not enough information to tell
By definition, Q = 0 for all adiabatic

processes.
pV = constant
21
Clicker question 9
along the adiabat from state a to state b. How much work, W, does the
system do on its environment?
a) 20 kJ
b) 20 kJ
p (kNm2)
c) 24 kJ
d) 24 kJ
e) 32 kJ
f) 32 kJ
g) not enough information to tell
16
adiabat
1
1
8 V (m3)
Eint = nCVT = n3RT (for a polyatomic gas)

first law: Eint = Q W

22
Clicker question 9
along the adiabat from state a to state b. How much work, W, does the
system do on its environment?
a) 20 kJ
b) 20 kJ
p (kNm2)
c) 24 kJ
d) 24 kJ
e) 32 kJ
f) 32 kJ
g) not enough information to tell
16
adiabat
W
1
1
Eint = 0 W = 3(nRT) = 3(pV)
a
8 V (m3)
= 3(16 8) = 24 W = 24 kJ
Eint = nCVT = n3RT (for a polyatomic gas)

first law: Eint = Q W

23
Summary of Processes
S1
S3
S2
S4
p1
p2
p3
p4
isentrop: S = 0
(reversible adiabat: Q = 0)
isobar: p = 0
isochor: V = 0
isotherm: T = 0
V1
d
V2
b = (p1, V2, T1, S1)

c = (p2, V2, T2, S2)
d = (p4, V2, T3, S3)
e = (p3, V1, T3, S4)
T1
c
e
a = (p1, V1, T2, S3)
T2
T3
V
free expansion (irreversible adiabat: Q = 0)

24
Summary of Processes
process
Eint =
nCVT
isobar
p(V2 V1)
pCp
(V2 V1)
R
pCV
(V2 V1)
R
nCp ln
isochor
VCV
(p2 p1)
R
VCV
(p p )
R 2 1
nCV ln
isotherm
V2
nRT ln
V1
V2
nRT ln
V1
isentrop
p1V1 p2V2
1
free
expansion
( )
( )
0
0
0
p2V2 p1V1
1
0
S
V2
V1
( )
p2
p1
( )
V2
nR ln
V1
( )
0
V2
nR ln
V1
( )
25
All processes on p-V, T-V, and T-S diagrams

p
T
a
T
V
T
S
V
V
An isobar (p), isotherm (T), isentrop (S), and isochor (V)

emanating from the same initial state (a) as manifest on
a p-V, T-V, and a T-S diagram.
26
Clicker question 10
Consider the p-V diagram below in which n = 1 mole of gas evolves reversibly from state a to state b along the path shown. What is the net change in
entropy? (Note, e = 2.71828 = Eulers number, and thus ln(e) = 1.)
p
a) Cp
c) CV
d) CV e
e) R
f) R e
g) no where near enough information!!
b) Cp e
some formulae, in case they help
S = nCp ln(V2) (isobar)

S
S
V1
p
= nCV ln 2
p1
V
= nR ln 2
V1
( )
( )
(isochor)
(isotherm)
27
Clicker question 10
Consider the p-V diagram below in which n = 1 mole of gas evolves revers
-ibly from state a to state b along the path shown. What is the net change in
entropy? (Note, e = 2.71828 = Eulers number, and thus ln(e) = 1.)
p
a) Cp
c) CV
d) CV e
e) R
f) R e
g) Yes there is!!
b) Cp e
Since S is a state variable, it doesnt

matter which path from a to b you
choose. Thus, choose the isobar.
S = nCp ln(V2) (isobar)

S
S
V1
p
= nCV ln 2
p1
V
= nR ln 2
V1
( )
( )
(isochor)
(isotherm)
28
Clicker question 11
The evolution of a system from state a to state b is shown on both the p-V
and T-S diagrams below. What is the change in internal energy?
p (Nm2)
2,000
T (K)
b
250
500
2 V (m3)
= nCV T
pV = nRT
10
Eint = Q W
30
S (JK1)
a) 2000 J
b) 2000 J
c) 5000 J
d) 5000 J
e) 7000 J
f) 7000 J
29
Clicker question 11
and T-S diagrams below. What is the change in internal energy?
p (Nm2)
2,000
T (K)
a
250
W = 2000 J
500
2 V (m3)
b
Q >~ 7500 J
10
30
Q ~ 7000 J
W = 2000 J
Eint = Q W
~ 5000 J
S (JK1)
a) 2000 J
b) 2000 J
c) 5000 J
d) 5000 J
e) 7000 J
f) 7000 J
30
Clicker question 12
and T-S diagrams below. About how many moles of gas are in the
system? (Take R = 8.)
p (Nm2)
2,000
T (K)
b
250
500
2 V (m3)
= nCV T
pV = nRT
10
Eint = Q W
30
S (JK1)
a) 0.5
b) 1
d) 2
e) not enough information to tell
c) 1.5
31
Clicker question 12
and T-S diagrams below. About how many moles of gas are in the
system? (Take R = 8.)
p (Nm2)
2,000
T (K)
b
500
250
2 V (m3)
10
30
pV = nRT
at state b:
pV = 2000
RT ~ 2000
n~1
S (JK1)
a) 0.5
b) 1
d) 2
e) not enough information to tell
c) 1.5
32
Clicker question 13
and T-S diagrams below. With n = 1 and Eint = 5000 J, this gas is:
p (Nm2)
2,000
T (K)
b
250
2 V (m3)
a) monatomic
500
CV ~ 12 (monatomic)
CV ~ 21 (diatomic)
CV ~ 25 (polyatomic)
10
b) diatomic
Eint = nCV T
30
S (JK1)
c) polyatomic

33
Clicker question 13
and T-S diagrams below. With n = 1 and Eint = 5000 J, this gas is:
p (Nm2)
2,000
T (K)
b
250
2 V (m3)
a) monatomic
500
CV ~ 12 (monatomic)
CV ~ 21 (diatomic)
CV ~ 25 (polyatomic)
10
b) diatomic
Eint = nCV T
30
S (JK1)
c) polyatomic

34
Three pictorial representations of an engine

p
Qin
Qin
ac
TH
W>0
Qout
c
V
In a complete thermodynamical cycle, gas

expands at high pressure
and compresses at low
pressure allowing work,
W, to be extracted in
each cycle.
expansion
stroke
ca
TC
Qout
QH = Qin
QC = Qout
Wout = W
compression
stroke
35
Maximum efficiency and the Carnot cycle

p
T
TH
T
a
Qin
TH
W>0
TC
Qout
S1
Qin
W>0
c
TC
S2 S
non-optimal thermo
-dynamical cycle for
an engine
d
S1
Qout
S1
a Q S2 adiabats
in
b
TC
c
isotherms
TH
Qout
S2 S
optimal thermodyn
-amical cycle for an
engine (Carnot cycle)
the Carnot engine cycle

on a p-V diagram
Note that for an engine, the thermodynamical cycle is always clockwise.

36
Refrigerators (heat pumps)

p
Qout
a Q S2 adiabats
out
W<0
Qin
S1
TC
V
For a refrigerator, the

cycle is always
counterclockwise.
Expansion happens at
low pressure,
compression at high
pressure and this takes
work. Heat is drawn in at
TC and expelled at TH.
isotherms
TH
d
Qin
c
V
QC = Qin
QH = Qout
Win = W
As for an engine, the most

optimal thermodynamical
cycle for a refrigerator is the
Carnot cycle traversed in
the counterclockwise
direction (opposite to the
engine).
37

Thermodynamics

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Thermodynamics

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Isothermal process on p-V, T-V, and p-T diagrams

Isochoric process on p-V, T-V, and p-T diagrams

Isobaric process on p-V, T-V, and p-T diagrams

first law of thermodynamics: Eint = Q W ( = nCVT )

ideal gas law: pV = nRT

first law of thermodynamics: Eint = Q W ( = nCVT )

ideal gas law: pV = nRT

first law of thermodynamics: Eint = Q W ( = nCVT )

ideal gas law: pV = nRT

first law of thermodynamics: Eint = Q W ( = nCVT )

ideal gas law: pV = nRT

first law of thermodynamics: Eint = Q W ( = nCVT )

ideal gas law: pV = nRT

first law of thermodynamics: Eint = Q W ( = nCVT )

ideal gas law: pV = nRT

first law of thermodynamics: Eint = Q W ( = nCVT )

ideal gas law: pV = nRT

first law of thermodynamics: Eint = Q W ( = nCVT )

ideal gas law: pV = nRT

first law of thermodynamics: Eint = Q W ( = nCVT )

ideal gas law: pV = nRT

first law of thermodynamics: Eint = Q W ( = nCVT )

ideal gas law: pV = nRT

first law of thermodynamics: Eint = Q W ( = nCVT )

ideal gas law: pV = nRT

first law of thermodynamics: Eint = Q W ( = nCVT )

ideal gas law: pV = nRT

Internal Energy (revisited)

degrees of specific heat at internal specific heat at

PHYS 1101, Winter 2009, Prof. Clarke

a = (p1, V1, T1)

a = (p1, V1, T0)

PHYS 1101, Winter 2009, Prof. Clarke

PHYS 1101, Winter 2009, Prof. Clarke

By definition, Q = 0 for all adiabatic

Eint = nCVT = n3RT (for a polyatomic gas)

ideal gas law: pV = nRT

Eint = 0 W = 3(nRT) = 3(pV)

Eint = nCVT = n3RT (for a polyatomic gas)

ideal gas law: pV = nRT

b = (p1, V2, T1, S1)

a = (p1, V1, T2, S3)

free expansion (irreversible adiabat: Q = 0)

PHYS 1101, Winter 2009, Prof. Clarke

All processes on p-V, T-V, and T-S diagrams

An isobar (p), isotherm (T), isentrop (S), and isochor (V)

some formulae, in case they help

S = nCp ln(V2) (isobar)

PHYS 1101, Winter 2009, Prof. Clarke

Since S is a state variable, it doesnt

S = nCp ln(V2) (isobar)

PHYS 1101, Winter 2009, Prof. Clarke

PHYS 1101, Winter 2009, Prof. Clarke

e) not enough information to tell

PHYS 1101, Winter 2009, Prof. Clarke

e) not enough information to tell

PHYS 1101, Winter 2009, Prof. Clarke

d) not enough information to tell

d) not enough information to tell

Three pictorial representations of an engine

In a complete thermodynamical cycle, gas

Maximum efficiency and the Carnot cycle

the Carnot engine cycle