Chapter 2
First Law of Thermodynamics
V⃗
2
ΔE univ =0 : (m/s2)
ΔE system + ΔE surroundings =0 m: (kg)
E: (J)
∆ E=∆ E k + ∆ E p =0
g: (m/s2)
1 E P =mgz
E K = m V⃗ 2 z: (m)
2
Work (W)
W=∫ F E dx W: (J) 1Pa m3=1J
FE w: (J/mol)
W =∫ d( Ax )=− ∫ P E dV
A Dependent of path
w=−∫ P E dv V2 V2
W =−∫ PE dV =−P E∫ dV =−¿ P E (V 2−V 1)¿
V1 V1
Heat (Q)
Q=n ∆ h Q: (J)
Sign convention:
Reversible process:
A process is reversible if, after the process occurs, the system can be returned to its original state
without any net effect on the surroundings.
Amount of reversibility: Amount of reversibility for compression:
wirrev w rev
ηexp = ηcomp =
efficiency of expansion wrev efficiency of compression process wirrev
wrev (exp) = - wrev (comp)
First law of thermodynamics for closed systems:
∆ U =Q+W ∆ U : (J)
∆ u=q+ w ∆ u : (J/mol)
First law of thermodynamics for open systems:
Flow work: dx
(Ẇ flow )in=−Pin A in dt =Pin A in V⃗ in=Pin ṅin v in
1
( Ẇ flow )in (Ẇ flow )out =−Pout ṅ out v out
( ẇflow )in = ṅin
=Pin v in
Ẇ=Ẇ shaft + Ẇ flow = Ẇ s + ∑ ṅin ( Pv )in + ∑ ṅ out (−Pv )out
in out
Energy balance for open systems:
If kinetic and potential energies can be neglected:
0=∑ ṅin hin − ∑ ṅ out hout + Q̇+ Ẇ S
in out
Enthalpy (h)
h≡u+Pv Cp: Appendix A. 2
hideal gas=u + RT
Closed system, Constant volume: Cv: Heat capacity at constant volume
CP: Heat capacity at constant pressure
∆ u=q
( )
Heat capacity at constant volume:
∂u
cv≡
∂T v
T2 T2
Δu=∫ c v dT =∫ [ a+ BT +CT + DT + ET ] dT
2 −2 3
T1 T1
2
∆ u :Change∈internal energy
h . H : Enthalpy
Constant pressure:
closed system, const P Δh=q
cP ≡ ( )∂h
∂T P
2 −2 3
c P =A + BT +CT + DT + ET
For liquids and solids:
c P =c v
For gasses:
cP ≡ ( ) (
∂h
∂T P
=
∂(u+ Pv )
∂T P
=
∂u
∂T ) ( ) P
+
∂( Pv )
∂T
Ideal gas:
c p =c v +R
Reversible, Isothermal expansion of an ideal gas
Ideal gas:
( ) ( )
nRT P2 P2
∆ U =0 V= W=nRT ln Q=−W =−nRT ln
P P1 P1
W=−∫ PdV
Adiabatic expansion of an ideal gas with constant heat capacity:
PV =nRT
cp cp cv R
k≡
cv
ln ( P1 V 1k )=ln ( P 2 V k2 ) PV k =const
nR 1
W= [ T −T ]
k −1 2 1
W= [ P V −P V ]
k−1 2 2 1 1
1 nR
ΔU =
k−1
[ P2 V 2 −P1 V 1 ] = [ T −T ]
k−1 2 1
3
Open-System balances and process equipment:
Thermodynamic cycles and the Carnot cycle:
4
5
6