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First Law of Thermodynamics and Processes635540941522169893 PDF
First Law of Thermodynamics and Processes635540941522169893 PDF
Thermodynamics (Ch.1)
Outline:
1. Internal Energy, Work, Heating
2. Energy Conservation the First Law
3. Quasi-static processes
4. Enthalpy
5. Heat Capacity
Internal Energy
The internal energy of a system of particles, U, is the sum of the kinetic
energy in the reference frame in which the center of mass is at rest and the
potential energy arising from the forces of the particles on each other.
Difference between the total energy and the internal energy?
system
boundary
system
U = kinetic + potential
environment
B
P
In equilibrium [ f (P,V,T)=0 ] :
U = U (V, T)
f
U = Nk BT
2
f
PV f
U = N in room k BT = N in room =
= PV
k BT 2
2
WORK
HEATING
U = Q + W
conservation of energy.
W.
T
An equivalent formulation:
Perpetual motion machines of the first type do not exist.
Quasi-Static Processes
Quasi-static (quasi-equilibrium) processes sufficiently
slow processes, any intermediate state can be considered
as an equilibrium state (the macroparamers are welldefined for all intermediate states).
Advantage: the state of a system that participates in a quasi-equilibrium
process can be described with the same (small) number of macro
parameters as for a system in equilibrium (e.g., for an ideal gas in quasiequilibrium processes, this could be T and P). By contrast, for nonequilibrium processes (e.g. turbulent flow of gas), we need a huge number
of macro parameters.
Examples of quasiequilibrium processes:
isochoric:
isobaric:
isothermal:
adiabatic:
V = const
P = const
T = const
Q=0
Work
A the
piston
area
W1 2 = P(T , V )dV
W = - PdV - applies to any
shape of system boundary
V1
dU = Q PdV
The work is not necessarily associated with the volume changes e.g.,
in the Joules experiments on determining the mechanical equivalent of
heat, the system (water) was heated by stirring.
V2
W1 2 = P (T , V )dV
V1
U = Q + W
P
P2
P1
V1
PV diagram
V2
d U = T d S P dV
y
- an exact differential
V
S
dz = Ax ( x, y ) dx + Ay ( x, y ) dy - it is an exact differential if it is
the difference between the values of some (state) function
z(x2,y2)
dz = z ( x + dx, y + dy ) z ( x, y )
z(x,y) at these points:
Ax ( x, y ) Ay ( x, y )
x
=
A necessary and sufficient condition for this:
x
y
z ( x, y )
z ( x, y )
z
If this condition
z
Ax ( x, y ) =
Ay ( x, y ) =
d z = dx + dy
holds:
x
y
x y
y x
T
f
z(x1,y1)
Problem
Imagine that an ideal monatomic gas is taken from its initial state A to state
B by an isothermal process, from B to C by an isobaric process, and from
C back to its initial state A by an isochoric process. Fill in the signs of Q,
W, and U for each step.
P,
105 Pa
2
T=const
Step
AB
--
BC
--
--
CA
B
C
f
U = Nk BT
2
V, m3
PV = Nk B T
W12 = 0
2
PV= NkBT2
PV= NkBT1
1
V1,2
3
Q12 = NkB (T2 T1 ) > 0
2
dU = Q12
isobaric
(= CV T )
( P = const )
2
1
V1
PV= NkBT2
PV= NkBT1
V2
5
Q12 = NkB (T2 T1 ) > 0
2
dU = W12 + Q12
(= CPT )
isothermal ( T = const ) :
PV= NkBT
W
V2
Wi f
dU = 0
V2
V1
V
= Nk BT ln i
Vf
V2
V
dV
= Nk BT ln 2
V
V1
V1
W12 = P (V , T )dV = Nk BT
V1
Q12 = W12
dU =W12
The amount of work needed to change the state of a thermally isolated system
depends only on the initial and final states and not on the intermediate states.
V2
V1
V2
PV = Nk BT
dV
V
PV= NkBT2
PV= NkBT1
V1
U=
dU =
f
Nk B dT = PdV
2
PdV + VdP = Nk B dT
2 dP
=0
1 + +
f
P
f
Nk BT
2
= 1+
2
PdV
PV
f
V
P
dV
dP
+
=0
V
P
V1
P1
PdV + VdP =
2 Adiabatic
f exponent
V
P
ln = ln 1 PV = P1V1 = const
P
V1
PV = P1V1 = const
P
2
V2
PV= NkBT2
PV= NkBT1
V1
V2
V2
V1
V1
W1 2 = P(V , T )dV =
V2
PV
1
+1
1 1
dV
PV
V
=
1
1
V
+ 1
V1
1 1
1
= PV
1 1
1 1
1 V2
V1
Prove W1 2 =
f
f
( PV ) = Nk B T = U
2
2
Quasi-Static
process
f
f
isobaric
U = Nk B T = P V
2
2
(P=0)
isochoric U = f Nk T = f P V
( )
B
2
2
(V=0)
isothermal
0
(T=0)
adiabatic U = f Nk T = f PV
( )
B
2
2
(Q=0)
Ideal gas
law
f +2
PV
2
PV
Vi V f
=
Ti T f
Pi Pf
=
Ti T f
f
( P )V
2
Nk B T ln
U
Vf
Vi
PV
i i = Pf V f
PV
i i = Pf V f
Problem
Imagine that we rapidly compress a sample of air whose initial pressure is
105 Pa and temperature is 220C (= 295 K) to a volume that is a quarter of
its original volume (e.g., pumping bikes tire). What is its final temperature?
Rapid compression approx. adiabatic, no time for the energy
exchange with the environment due to thermal conductivity
P1V1 = Nk BT1
P2V2 = Nk BT2
P2 =
P1V1 = P2V2
P1V1
V2
P1V1
P1V1
Nk
T
=
=
T2
B 2
V2 1
T1
V1
T2 = T1
V2
V1
V2
1
T1 V1
= T2 V2
also
P 1 / T = const
= const
- poor approx. for a bike pump, works better for diesel engines
T2
T1
2.
TV 1 = const
V increases
T decreases (cooling)
TV 1 = const
The Enthalpy
Isobaric processes (P = const):
dU = Q - PV = Q -(PV)
Q = U + (PV)
H U + PV - the enthalpy
Q=U
isobaric:
Q=H
in both cases, Q
does
not
depend on the
path from 1 to 2.
f
The enthalpy of an ideal gas: H = U + PV =
Nk BT + Nk BT = + 1 Nk BT
2
2
(depends on T only)
Heat Capacity
The heat capacity of a system - the amount of energy
transfer due to heating required to produce a unit
temperature rise in that system
T
C is NOT a state function (since Q is not a
state function) it depends on the path
between two states of a system
f1
Q
T
f2
f3
T1+dT
T1
( isothermic C = , adiabatic C = 0 )
C
c
m
CV and CP
C=
Q
dT
T V constant volume
dU + PdV
dT
H
CP =
T P
f
H
=
+
1
U = Nk BT
Nk BT
2
2
f
f
f
CP = + 1 nR
CV = Nk B = nR
2
2
2
# of moles
For one mole of a
monatomic ideal gas:
CV =
3
5
R CP = R
2
2
Another Problem
During the ascent of a meteorological helium-gas filled balloon,
its volume increases from Vi = 1 m3 to Vf = 1.8 m3, and the
pressure inside the balloon decreases from 1 bar (=105 N/m2) to
0.5 bar. Assume that the pressure changes linearly with volume
between Vi and Vf.
(a) If the initial T is 300K, what is the final T?
(b) How much work is done by the gas in the balloon?
(c) How much heat does the gas absorb, if any?
Pi
Pf
Vi
Vf
(a)
PV = Nk B T
(b) WON
PV
T=
Nk B
0.5bar 1.8m 3
= 300K
= 270K
T f = Ti
3
1bar 1m
Pi Vi
Pf V f
Vf
Vf
Vi
Vi
Vf
WON = WBY WBY = P(V )dV = (0.5 0.8 bar m3 + 0.5 0.4 bar m3 ) = 0.6bar m3 = 6 10 4 J
(c)
U = Q + WON
Vi
Q = U WON = NkB (T f Ti ) WON = Pi Vi f 1 + WBY = 1.5 105 J ( 0.1) + 6 104 J = 4.5 104 J
2
2
Ti