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reservoir
reservoir
Heat
Heat
Work
Work
∫ pdV
V2
⇒W =
V1
Work in pV diagrams
∆U = Q − W
Conservation of energy
1st Law of Thermodynamics
Heat is negative Work is negative
when it leaves when it is done on
the system the system
dU = dQ − pdV
Conservation of energy
State Functions
(a) (b) (c)
W = ∫ pdV
Vf
W = p2 (V2 − V1 ) W = p1 (V2 − V1 ) Vi
• The work done by a system depends on the initial and final states and
on the path it is not a state function.
• Amount of heat transferred also depends on the initial, final, and intermediate
states it is not a state function either.
State Functions
∆U = Q − W = U 2 − U 1
The internal energy U is a state function: the energy gain
(loss) only depends on the initial and final states, and not
on the path.
Even though Q and W depend on the path, ∆U does not!
CPS question
This pV–diagram shows two
ways to take a system from state
a (at lower left) to state c (at
upper right):
• via state b (at upper left), or
• via state d (at lower right)
For which path is W > 0?
A. path abc only B. path adc only
C. both path abc and path adc
D. neither path abc nor path adc
E. The answer depends on what the system is made of.
CPS question
A system can be taken from
state a to state b along any of
the three paths shown in the pV–
diagram.
If state b has greater internal
energy than state a, along which
path is the absolute value |Q| of
the heat transfer the greatest?
Q=0 → U2 – U1 = -W
W=0 → U2 – U1 = Q
∆U=0,Q =-W only for ideal gas. Generally ∆U,Q, W not zero
any energy entering as heat must leave as work
Thermodynamic processes
First Law for Several Types of Processes
Isolated systems: Cyclic processes Adiabatic processes
P
i, f
Q =W = 0 V
initial state = final state
→ ∆U = 0 Q=0
∆U = 0
→ Ui = U f → ∆U = −W
→ Q =W Expansion: U decreases
The internal energy
Energy exchange between Compression: U increases
of an isolated systems
remains constant “heat” and “work”
More about cyclic processes
P
i, f
∫ pdV
V2
→ W = ∫ pdV = 0
2 p2V = nRT2
V2
V1
1
p1V = nRT1
Q = CV (T2 − T1 )
(CV: heat capacity
= CV ∆T at constant volume)
V1,2 V
∆U = Q − W
→ ∆U = Q = CV ∆T
reservoir
→ ∆U = Q − W
reservoir
= C P ∆T − p ∆V
Heat During an isobaric expansion process,
heat enters the system. Part of the heat is
Work used by the system to do work on the
environment; the rest of the heat is used
to increase the internal energy.
Ideal gas: isothermal process
P 1 pV = nRT
Isothermal process: T = constant
2 ∆T = 0 ⇒ ∆U = 0
W = ∫ pdV = ∫
V2 V2 nRT
dV
V1 V1 V
= nRT ∫
V1 V2 V
V2dV
Expansion: V1 V
heat enters the system
all of the heat is used by the system V2
to do work on the environment. = nRT ln
V1
Compression:
V2
the work done on the system increases
its internal energy,
→ Q = W = nRT ln
all of the energy leaves the system at V1
the same time as the heat is removed.
Heat capacities of an Ideal gas
Consider an isobaric process p=constant
Q p = C p ∆T
From the 1st Law of Thermodynamics:
dQ p = C p dT = dU + pdV
but ⇒ C p dT = CV dT + pdV
dU = CV dT
From the Ideal gas law:
⇒ C p dT = CV dT + nRdT ⇒ C p = CV + nR
Heat capacities of an Ideal gas
C p = CV + nR
f +2
f = #degrees f ⇒ Cp = nR
of freedom CV = nR 2
2
Cp f +2 f f +2
⇒ = nR / nR =
CV 2 2 f
For a monoatomic gas f=3
5 Cp
⇒ C p = nR; = 5 / 3 = 1.67
2 CV
Molar heat capacities of various gases at (25 C)
Gas Cp Cv Cv/R Cp-Cv (Cp-Cv)/R
Monoatomic
He 20.79 12.52 1.51 8.27 0.99
Ne 20.79 12.68 1.52 8.11 0.98
Ar 20.79 12.45 1.50 8.34 1.00
Kr 20.79 12.45 1.50 8.34 1.00
Xe 20.79 12.52 1.51 8.27 0.99
Diatomic
N2 29.12 20.80 2.50 8.32 1.00
H2 28.82 20.44 2.46 8.38 1.01
O2 29.37 20.98 2.52 8.39 1.01
CO 29.04 20.74 2.49 8.40 1.00
Polyatomic
CO2 36.62 28.17 3.39 8.45 1.02
N2O 36.90 28.39 3.41 8.51 1.02
H2S 36.12 27.36 3.29 8.76 1.05
Ideal gas: adiabatic process
Adiabatic process: Q = 0
V1 V1
V2 V1 pV = Nk BT
V
→ d ( pV ) = d ( nRT )
→ pdV + Vdp = nRdT
2
dU = − dW = − pdV pdV + Vdp = − pdV
f
→ CV dT = − pdV
f
→ n RdT = − pdV
2
∫p1 p ∫V1 V = 0
dp
p V dV
+ γ
p V
→ ln + γ ln = 0
p1 V1
pV γ γ γ
→ ln γ = 0 → pV = p1 1 = constant
V
p1V1
Ideal gas: adiabatic process (contd)
P γ
W = − ∆U = − nCV ∆T
2 pV = constant
= nCV (T1 − T2 )
CV
1 = ( p1V1 − p2V2 )
R
V2 V1 1
V = ( p1V1 − p2V2 )
γ −1
Using:
γ γ
pV = p1V1 = constant
1 1 1
→ W = p1V1
γ
γ −1 − γ −1
(γ − 1) V1 V2
Ideal gas: adiabatic process (contd)
γ
P pV γ = p1V1 = constant
2 pV γ = constant
1 p1V1 = nRT1 p1 V1 T1
→ =
V2 p2V2 = nRT2 p2 V2 T2
V1 V γ
γ γ p V
p1V1 = p2V2 → 1 = 2γ
p2 V1
V2γ −1 T1
→ γ −1 =
V1 T2
γ −1 γ −1
or T1 V1 = T2 V2 = constant
Ideal gas: adiabatic process (contd)
γ
P γ
pV = constant pV γ = p1V1 = constant
2
γ −1 γ −1
T1 V1 = T2 V2 = constant
1
pV = nRT
p1V1 1 1
V2 V1 γ
γ −1
V
W= γ −1 −
(γ − 1) V1 V2
A. equal to W12.
B. less than W12.
C. greater than W12.
D. either A., B., or C., depending on the ratio of V2 to V1.
Summary
Quasi-static
process
Character ∆U Q W
isochoric V = constant ∆U = Q Q = CV ∆T W =0