ENERGY BALANCE

Mass is one kind of energy (Einstein, relativity theory)

E = mc2
 
You learn this in thermodynamics! 

1). Internal energy (energi dakhil): U, E

All energy inside the system: atom, electron motion,
etc. State function
 
2). Enthalpy: H (h)
Internal energy + energy to compensate “pressure”
from the surrounding.
State function
3). Work: W
Such as mechanical work
Path function
 
4). Heat: Q
Path function
 
5). Kinetic energy

6). Potential energy

 First thermodynamic law

Nonflow process
 Q = U2 – U1 + W = ∆U + W
Work can be W = ∫pdV

U1 p U2 p

Q
 Flow process
2

M v2 P2 U2

1 -W
M v1 P1 U1

Total energy in = total energy out

U1 + P1V1 + ½ Mv12 + MgZ1 + Q – W = U2 + P2V2 + ½ Mv22 + MgZ2

Enthalpy : H = U + PV
 H1 + ½ Mv12 + MgZ1 + Q – W = H2 + ½ Mv22 + MgZ2
 ∆H + ½ M∆v2 + Mg∆Z = Q – W
In chemical processes, thermal energy dominates
→ ∆H = Q – W
Example:
1 kg of water falls from 100 m high  temperature rise?
 Air
4
1

3
Combustion
chamber Fuel

Condition: Enthalpy (H, BTU/mol)

1: 60°F 1033
2: 340°F 2992
3: 1000°F 7823
4: 640°F 5142
 Compressor work W? Turbine work? Efficiency?
 Enthalpy
solid liquid vapor

 Sensible heat: temperature changes, no change of

phase
 Latent heat: phase change (freezing, vaporization)
 Heat of formation: chemical bond between atoms
 Heat of mixing

• Do we need to know the absolute value of enthalpy?

• Reference temperature
Sensible heat
Q = M ∫CpdT
Specific heat Cp = f(T)  Cp = a + bT + cT2 + dT3
Reference temperature 298K (25°C)
Cp mean: average Cp from ref temp to T  Cp,mean
• Latent heat: λ or hv (vaporization)

H A

vapor
B

liquid

Temperature T Tref

HA = MA.(CpA).(T – Tref)
HB = MB[Cpl,B.(Tb-Tref) + λv + Cpv,B.(T-Tb)]
Heat of formation: hf
• Bond between atoms, groups,……
• Reference temperature: 298K  hf,298 or hf°
• For “atom”, such as S, O2, N2, C  hf° = 0
• Heat of reaction:  exothermic, endothermic
aA + bB  dD + eE (stoichiometric coef.!)
ΔHR = ∑(nihfi)product - ∑(njhfj)reactant
ΔHR = dhf,D + ehf,E – (ahf,A + bhf,B)
Be careful with the phase of component !
• hf,T = hf,298 + ∫CpdT = hf,298 + Cp,mean(T – 298)
Example
Gas phase reaction:
(1)CH4 + H2O → CO + 3 H2
(2)CO + H2O → CO2 + H2
Reactor feed H2O : CH4 = 2 : 1 (mol/mol). All CH4 is reacted.
Reactor effluent contains CO 17.4%.
T-in = 600K, T-out = 1300K.

hf,298 (cal/mol) Cp 600K Cp 1300K

CH4 - 17,889 10.46 ---

H2 O - 57,798 8.32 9.28

CO - 26,416 -- 7.60
CO2 - 94,052 -- 11.97

H2 --- -- 7.12
 Heat of combustion
• Heat of oxidation reaction: ΔHc
• Reaction product: CO2, H2O, SO2 (complete combustion)
• Higher heating value (HHV) or GHV  H2O liquid
• Lower heating value (LHV) or NHV  H2O vapor