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For an open system, the energy balance equation is;

Net change in energy = Energy of mass entering – Energy of mass leaving ± Energy flow into or out
the system the system of the system

Consider time dependence:

d(H) = d(H)mass input - d(H)mass output ± d(H)energy flow
dt dt dt dt

Consider a fluid flows in a rate d(M)/dt and flows out at a rate d(M)/dt, then the change of enthalpy
due to this flow is
d(H) = Cpm d(T) + CpT d(M)
dt dt dt

Conduction
Conduction – is the transfer of heat through a material by molecular diffusion (spread out) due to a
temperature gradient.
Eqn: Fourier’s Law
d(H) = - htc A d(T)
dt dx
where;
d(H) = rate of change of enthalpy, in kJ/s or kW
htc = thermal conducivity, in kJ/s.m.K or kW/m.K
d(T) = change of temperature through a distance, in K/m
A = surface area, in m2

Convection
Forced convective heat transfer – is the transfer of thermal energy by means of large-scale fluid motion such
as a flowing river or aquifer or the wind blowing.
For convective heat transfer between a fluid at a temperature, Tf, and a solid surface at a temperature Ts,
Eqn:
d(H) = hC A ( Tf – Ts )
dt
where;
d(H) = rate of change of enthalpy
dt
hC = convective heat transfer coefficient, In kJ/s.m.K
A = surface area, in m2

Radiation
Although both conduction and convection require a medium to transport energy, radiant energy is
transported by electromagnetic radiation. The radiative transfer of heat involves two processes: (a) the
absorption of radiant energy by an object, and (b) the radiation of energy by that object. The change in enthalpy
due to the radiative heat transfer is the energy absorbed minus energy emitted and can be expressed as
d(H) = Eabs - Eemitted
dt
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where;
E = hf = h c
λ
h = Planck’s constant, ( 6.63 x 10-34 J.s )
c = speed of light, ( 3.0 x 108 m/s )
λ = wavelength
f = frequency
The electromagnetic wave emitted when an electron makes a transition between two energy levels is called
photon. When the frequency is high, the energy emitted is high. Planck’s law also applies to the absorption of a
photon of energy.
Every object emits thermal radiation. The amount of energy radiated depends on the wavelength, surface
area, and the absolute temperature of the object. The maximum amount of radiation that an object can emit at
a given temperature is called blackbody radiation. An object that radiates the maximum possible intensity for
every wavelength is called a blackbody.
Actual objects do not emit or absorb as much radiation as a blackbody. The ratio of the amount of radiation
an object emits to that a blackbody would emit is called emissivity (ε).
For the radiant energy of a blackbody is

E B = σ T4
where;
EB = blackbody emission rate, in W/m2
σ = Stephan-Boltzmann constant ( 5.67 x 10-8 W/m2 . K4
T = absolute temperature, in K

Example:
A Peach company dips peaches in boiling water (100oC) to remove the skin (a process called blanching)
before canning them. The wastewater from this process is high in organic matter and it must be treated before
disposal. The treatment process is a biological process that operates at 20 oC. Thus, the wastewater must be
cooled to 20oC before disposal. Forty cubic meters (40 m3) of wastewater is discharged to a concrete tank at a
temperature of 20oC to allow it to cool and that the concrete tank has a mass of 42,000 kg and a specific heat
capacity of 0.93 kJ/ kg.K. How long will it take for the wastewater and concrete tank to come to the desired
temperature of 20oC if radiative cooling and convective cooling are considered?
Assume that he average temperature of the wastewater and concrete tank while cooling between 85 oC and
20oC is 52.5oC and that the mean radiant temperature of the surroundings is 20 oC, that both the cooling tank and
the surrounding environment radiate uniformly in all directions, that their emissivities are the same (0.90),
that the surface area of the tank including the open water surface is 56 m 2, and that the convective heat transfer
coefficient is 13 J/s.m2.K.
Given:
Twastewater = 100oC = 100 + 273 = 373 K A = 56 m2
Vwastewater = 40 m3 hC = 13 J/s.m2.K
ρwater = 1000 kg/m3
Cv = 0.93 kJ/kg.K (concrete)
Ttank = 20oC = 20 + 273 = 293 K
mtank = 42,000 kg
Taverage = 52.5oC = 52.5o + 273 = 325.5 K
ε = 0.90
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Required: The time for the wastewater and the tank to have the desired temperature of 20 oC.
Figure: Consider the concrete tank.

wastewater
at 100oC
V = 40 m3
concrete
tank

wastewater
at 20oC

Eqn: ∆H = mCp∆T
ρ = m / V ; m = ρ (V)
EB = εσ( T4)
d(H) = hC A ( Tf – Ts )
dt
d(H) = EB A
dt
Solution: Solving the time t.
for the change (loss) of enthalpy of wastewater from 52.5 oC to 20oC
∆H = mCP (∆T)
= (1000 kg/m3)(40 m3)(4.186 kJ/kg.K)(325.5 K – 293 K)
= (167,440 kJ/K)(32.5 K)
∆H = 5,441,800 Kj

for the change (gain) of enthalpy of concrete tank from 52.5 oC to 20oC
∆H = mCP(∆T)
= (42,000 kg)(0.93 kJ/kg.K)(325.5 K – 293 K)
= (39,060 kJ/K)(32.5 K)
∆H = 1,269,450 kJ

for the total change of enthalpy

∆HT = 5,441,800 kJ + 1,269,450 kJ = 6,711,250 kJ

for the time to cool down the wastewater and concrete tank by radiation (emission) to 20 oC, then
the emissivities of tank and environment is the same. The net radiation is
EB = εσ [ (Tconcrete)4 – (Tenvironment)4 ]
= (0.90)(5.67 x 10-8W/m2.K4)[ (325.5 K)4 – (293 K)4 ]
= (5.103 x 10-8 W/m2.K4)( 1.12 x 1010 K4 – 7.37 x 109 K4)
= (5.103 x 10-8 W/m2.K4)(3.83 x 109 K4)
EB = 196.7 W/m2

for the rate of heat loss due to surface area

d(H) = EB A = 196.7 W/m2 (56 m2) = 11,018 W or J/s
dt
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 for the convective cooling rate
d(H) = hC A (Tf – Ts)
dt
= (13 J/s.m2.K)(56 m2)( 325.5 K – 293 K)
= (728 J/s.K)(32.5 K)
d(H) = 23,660 J/s
dt

for the time to cool down to 20oC is

Total Enthalpy = (Total Energy rate due to radiation and convection)( time)
time = Total enthalpy
Total energy rate
t = 6,711,250 kJ
11,018 J/s + 23,660 J/s
= 6,711,250,000 J
34,678 J/s
t = 193,530 s = 2.24 days (answer)

Second Law of Thermodynamics

The second law of thermodynamics states that energy flows from a region of higher concentration to one
of lesser concentration, not the reverse, and that the quality degrades as it is transformed. Heat always flow
spontaneously from a hotter body to a colder one; gases seep through an opening spontaneously from a region
of higher pressure to a region of lower pressure. The second law recognizes that order becomes disorder, that
randomness increases, and that structure and concentration tend to disappear. It foretells elimination of
gradients, equalization of electrical and chemical potential, and levelling of contrasts in heat and molecular
motion unless work is done to prevent it. Thus, gases and liquids left by themselves tend to mix, not to unmix;
rocks weather and crumble; iron rusts.
The degradation of energy as it is transformed means that enthalpy is wasted in the transformation. The
fractional part of the heat which is wasted is termed unavailable energy. A mathematical expression called the
change in entropy is used to express this unavailable energy.
Eqn:
∆s = m Cp ln T2
T1
where
∆s = change in entropy
m = mass
Cp = specific heat at constant pressure
T1, T2 = initial and final absolute temperature
ln = natural logarithm
By the second law, entropy increases by any transformation of energy from a region of higher concentration
to a lesser one. The higher the degree of disorder, the higher the entropy. Degraded energy is entropy,
dissipated as waste products and heat.
Efficiency(ƞ) or, perhaps lack of efficiency is another expression of the second law. Sadi Carnot (1824) was
the first to approach the problem of the efficiency of a heat engine (e. g. , a steam engine) in z truly fundamental
manner. He described a theoretical engine, now called a Carnot engine. In his engine, a material expands against

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a piston that is periodically brought back to its initial condition so that in any one cycle the change in internal
energy of this material is zero, that is U2 – U1 = 0, and the first law of thermodynamics reduces to
W = Q 2 – Q1
where
Q1 = heat rejected or exhaust heat
Q2 = heat input
Thermal efficiency is the ratio of work output to heat input. The output is mechanical work. The exhaust heat
is not considered part of the output.
ƞ = W
Q2
where
W = work output
Q2 = heat input
so
ƞ = Q2 – Q 1
Q2
for maximum efficiency;
ƞmax = 1 – T1
T2

Example:
The Michigan State University power plant is rated at 61 MW. Calculate the efficiency of power generation if
anthracite coal with a heating value of 32 MJ/kg is fired at a rate of 5.45 kg/s. Use one hour as the time interval
for computation.
Given:
P = 61 MW
m = 5.45 kg/s
t
Q = 32 MJ/kg
Required: The efficiency of the power generation
Figure: Consider the power plant

Qinput Power
Plant

Equation: ƞ = W
Q2
Solution: Solving the efficiency (ƞ)
for the ƞ: ƞ = W ; W = P (t)
Q2
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but for one hour, the heat input Q is
Qinput = (32 MJ/kg)(5.45 kg/s)(3,600 s/h)(1h) = 627,840 MJ
for 1 kWh = 3,600 000 J = 3.6 MJ
so Qinput = 627,840 MJ
3.6 MJ /kWh
Qinput = 174,400 kWh = 174,400 kWh x 0.001 MW = 174.4 MWh
1.0 kW

then, ƞ = W = P(t)
Q Q
= 61 MW (1 h)
174.4 MWh
ƞ = 0.3498 or 34.98% (answer)