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Chapter 20
Entropy and the Second
Law of Thermodynamics
•Thermal expansion cracking the nut. (Strength of electrical forces)
•Jug O' Air (Inflate with bike pump and watch temp. rise)
p/T = constant
1m
Avogadro’s Number
NA=6.02 x 1023 atoms or molecules in one mole of any gas.
One mole is the molecular weight in grams. It is
also called the molar mass.
1 mole of air contains 29 gms
p = nRT / V
V = volume in units of m 3
n = number of moles
T = temperature in units of K
R = 8.31J/moles ⋅ K Called the gas constant
pV = NkT
At high gas densities you must add the Van der Waal corrections
where a and b are constants.
NkT a 2
p= −( )
V −b V
Lets use the ideal gas law to understand the 1st law of Thermodynamics
ΔEint = Q − W
Work done by an ideal gas
Always keep this picture in
your head. Memorize it!!
W = ∫ Fdx
F
W = ∫ A
Adx
W = ∫ pdv
ΔEint = Q − W
pV diagram
For an isothermal process or constant temperature.
This is an equation of a hyperbola.
pV = nRT
nRT constant
p= =
V V
What is the work done by an ideal gas when
the temperature is constant?
pV = nRT For constant temperature.
∫
Vf
W = Vi
pdV
nRT
∫
Vf
W = dV
Vi V
constant
dV
= nRT [ lnV ]Vif
Vf
W = nRT ∫
V
Vi V
Vf
W = nRT ln
Vi
What is the work done by an ideal gas when
the temperature is constant?
Vf
W = nRT ln
Vi
pV = nRT
W = p(V f − Vi )
For a constant pressure process
19
W = (1)(8.31)(310)ln( )
12
= 1180J W = The area under the curve.
ΔEint = Q − W
What’s Next
Vf T
W = nR ∫ dV
Vi V
ΔEint = Q − W
Fx mvx2 / L
p= 2 = = m(v 2
x ) / L3
Due to one molecule
L L2
3RT
v rms =
M
3RT 3RT
K avg = 12 m =
M 2N A
K avg = 32 kT
1
λ=
2πd 2 N /V
Find λ
pV = NkT
1
λ= N
=
p
2πd 2 N /V V kT
λ = 1.1 × 10 −7 m = 380d
What is v, the speed of a molecule in an ideal gas?
Use the rms speed.
3RT
v rms = vrms =
3(8.31)(300)
= 483m / s
M 0.032
f = vrms / λ
483
f = −7
= 4.38 × 10 9
/s
1.1 × 10
0
P(v)dv = 1 vp
∫
∞
v avg = 0
vP(v)
∫
∞
v rms = (v 2 ) avg = v 2 P(v)dv
0
Therefore, 3 3
ΔEint = nN A kT = nRT
2 2
• We know ΔEint
• We know W
• We have ΔEint = Q − W
3
But ΔEint = ( )nRΔT from above
2
Using Q= ΔEint
3
nCV ΔT = nRΔT
2
3
CV = R = 12.5J / mol ⋅ K
2
Cv for different gases
The internal energy for any ideal gas can be written
as long as the correct CV is used.
Eint = nCV T
The internal energy and change in internal energy only depends
on the temperature change. That is it only depends on the endpoints
and not the path. This confirms what we said earlier about the first law.
Also note that Q and W depend on the path but the difference Q-W
is path independent. See Fig 19-9 in text.
Q = nC p ΔT
ΔEint = Q − W
W = pΔV
pV = nRT
ΔEint = nCV ΔT
nCV ΔT = nC p ΔT − nRΔT
CV = C p − R
Note we do not let any heat get exchanged between system and environment
We want to show
pV γ = constant
Cp
γ =
CV
for Q = 0 thermodynamic processes
Adiabatic Expansion of an Ideal Gas: Q = 0
ΔEint = Q − W
Q=0
dE int = −W = − pdV
dE int = nCV dT
− pdV = nCV dT
ndT = − pdV /CV
From the ideal gas law pV = nRT
pdV + Vdp = nRdT = n(CP − CV )dT
pdV + Vdp = (CP − CV )ndT = −(CP − CV ) pdV /CV
CP
pdV + Vdp = −( −1) pdV
CV
dP CP dV
+ =0
P CV V
Adiabatic Expansion of an Ideal Gas: Q = 0
dP dV
∫ P +γ ∫ V = 0
ln P + γ lnV = constant
ln PV γ = constant
PV γ = constant
Cp
γ =
CV
PROBLEM 20-58E
γRT
Show that the speed of sound in a ideal gas for an adiabatic process is v s =
M
Recall B dp dp p
vs = B = −V = − γ B=γ p
ρ dV dV V
γp γ nRT / V γ RT pV γ = constant
vs = = =
ρ ρ M
γRT γ 3RT γ Cp 5
vs = = = v rms γ = =
Also M 3 M 3 CV 3
For helium at 300 K, the molecular speed is vrms= 1370 m/s and. Then
the predicted speed of sound in helium is 1021 m/s. The measured
value is 965m/s
Problem 20-61P
One mole of an ideal monatomic gas
traverses the cycle shown in the figure.
(a) Find Q, ΔΕint , and W for each process.
1 2 constant volume
W =0
ΔEint = Q
3
ΔEint = nCV ΔT = n RΔT = (1mol)(1.5)(8.314J / mol ⋅ K )(600 − 300)K
2
ΔEint = Q = 3.74 × 10 3 J
2----3 Q=0
3
ΔEint = nCV ΔT = n RΔT = (1mol)(1.5)(8.314J / mol ⋅ K )(455 − 600)K
2
ΔEint = −1.81 × 10 3 J
W = Q − ΔEint = 1.81 × 10 3 J
3 1 constant pressure
3 5
C p = Cv + R = R+ R= R
2 2
5
Q = nC p ΔT = n RΔT = (1mol)(2.5)(8.314J / mol ⋅ K )(300 − 455)K
2
Q = −3.22 × 10 3 J
3
ΔEint = nCV ΔT = n RΔT = (1.5)(8.314)(300 − 455) = −1.93 × 10 3 J
2
W = Q − Eint = [ (−3.22) − (−1.93)] × 10 3 J = −1.29 × 10 3 J
(b) Find the pressure and volume at points
2 and 3.
The pressure at point 1 is
1 atm = 1.013 x 105 Pa.
P1 1.013 × 10 5
nRT3 (1)(8.314)(455) −2
V3 = = = 3.43 × 10 m 3
P3 1.103 × 10 5
Equipartition Theroem
Equipartition Theorem: Each molecule has 1/2kT
of energy associated with each independent
degree of freedom
f f
Eint = kt = nRT
2 2
CV = (3/2) R for monatomic gas (f=3)
CV= (5/2) R for diatomic gas (f=5)
CV = (3) R for polyatomic gas (f=6)
CP = CV + R
CV for a diatomic gas as a function of T
Below 80 K only
translational modes can be
excited
Above 80 K rotational modes
begin to get excited
f
dQ
T2 > T 1 ΔS = S f − Si = ∫ T
i
T2 T1
The statistical nature of entropy
• Black beans on the right
• White beans on the left
• Add some energy by shaking them up and they
mix
• They never will go back together even though
energy of conservation is not violated.
• Again what controls the direction?
• Assume that entropy is a state property like pressure and volume
and only depends on the initial and final state, but not on how it got
there . Then the change in entropy is defined as:
f
dQ
ΔS = S f − Si = ∫ T
i
Note that units are Joule per kelvin and the sign is the same as Q
since T > 0
• However, the above formula can only be used to calculate
the entropy change if the process is reversible..
W
ΔS =
T
f
W= ∫ pdV
i
pV = nRT
f
dV Vf Vf
W = ∫ nRT W = nRT ln ΔS = nR ln
i
V Vi Vi
Example: Four moles of an ideal gas undergo a reversible
isothermal expansion from volume V1 to volume V2 = 2V1 at
temperature T = 400K.
a) Find the work done by the gas.
b) Find the entropy change of the gas?
c) Find the entropy change if the process is adiabatic
instead of isothermal
2V1
W = nRT ln = nRT ln 2 = (4mol)(8.31J / molK )(400K )ln 2 = 9.22x10 3 J
V1
b) Find the entropy change of the gas.
We just showed that
W
ΔS =
T
W 9.22x10 3 J
ΔS = = = 23.1J / K
T 400K
ΔQ = 0 ΔS = 0
For an ideal gas in any reversible process where
the temperature and volume may change, the entropy
change is given by the following:
f
dQ
ΔS = S f − Si = ∫ T
i
dEint = dQ − dW
Vf Tf
ΔS = nRln + nCV ln
Vi Ti
f
dQ
ΔS = ∫
i
T
Vf
ΔS = nR ln = nR ln 2 = k ln 2
Vi
Statistical View of Entropy
Boltzman Entropy Equation
S = k ln W
n1=4 n2=2
n1=3 n1=3
N=6
Label Percent n1 n2 W S
age 10-23J/K
I 100 6 0 1 0
II 83 5 1 6 2.47
III 67 4 2 15 3.74
IV 50 3 3 20 4.13
V 33 2 4 15 3.74
VI 17 1 5 6 2.47
VII 0 0 6 1 0
N!
S = k ln W W= N!=6x5x4x3x2x1
n1 !n2 !
N!
W=
n1 !n2 !
6! 6x5x4x3x2x1 6x5
W= = = = 15
4!2! 4x3x2x1x2x1 2
This shows the number of microstates
available for each configuration
25 N=1022 molecules
Number of Microstates
N=6 molecules
20
15
W
10
0
0 50 100
Percentage of Molecules in Left
Half
Statistical View of Entropy
Starting from the Boltzman equation S = k ln W
show the same result.
N!
Wi == =1 N 0 Initial system
N !0!
N!
Wf =
N N N/2 N/2 Final system
( )!( )!
2 2
0
ΔS = k lnW f − k lnWi
N!
ΔS = k lnW f = k ln( ) k ln 2 Same result as that obtained
N N from the gas law.
( )!( )!
2 2
Use Stirling formula
ln N ! ≈ N ln(N ) − N For very large N
N!
ΔS = k lnW f = k ln( )
N N
( )!( )!
2 2
N! N
ln( ) = ln(N !) − 2 ln(( )!) = ln 2
N N 2
( )!( )!
2 2
ΔS = k ln 2 = nR ln 2
2nd Law of Thermodynamics
ΔS ≥ 0
Summer 2008
Dramatic-Why does the stick break so violently and leave the glass intact?
Breaking Broomstick Demo
vLE 2FΔt MASS: m
LENGTH: L
-Support each pin with a wine glass, coke can, block of wood, etc.
Need clearance
-Use a hacksaw to etch it around the circumference; avoid stick fracturing due to
other weakness.
-Raise striking stick and hit the center as hard as you can; follow through