Section 2

Material and
Heat Balances

BE 242 Engineering Analysis and Design

by
B. Brian He
 BE 242 Engineering Analysis & Design

2.1 Conservation of Mass and Material Balance

Mass balance is a very powerful tool in engineering analysis. Many complex

situations are simplified by looking at the movement of mass and equating what comes
out to what goes in.

2.1.1 Terms used in material balances

A system is any matter identified for investigation. It separates its surroundings by
a boundary. The boundary may be actual and physical, such as the walls of an
evaporator or a solution preparation tank, or just imaginary. If there is no materials move
across the boundary, the system is a closed system; if a system exchanges materials with
its surroundings, it is an open system.
A process is system that causes material changes and the commonly used
processes include:
(a) A batch process is a process that operates in a closed system. All materials
are added to the system at the start of the process; the system is then closed
and products removed only when the process is complete.
(b) A semi-batch process is a process that has either input or output of mass, but
not both at the same time.
(c) A fed-batch process is a process that permits materials being added to the
system, but not from the system or no output.
(d) A continuous process is a process that allows matter to flow in and out of
the system. If the feeding mass flow rates are equal to those of the effluents,
the continuous processes can be operated indefinitely without any
accumulations.
If the parameters of a process, such as temperature, pressure, volume, mass, etc. do
not vary with time, the process is at steady state. Contrary to steady state processes,
batch, fed-batch and semi-batch processes could be operated indefinitely. Mass changes
with time in fed-batch and semi-batch processes. Some properties of the system also
change although the total mass keeps unchanged. Such processes, i.e., batch, fed-batch
and semi-batch processes, are transient processes or unsteady-state processes. On the
other hand, continuous processes can be steady state or transient. Continuous processes
will undergo unsteady-state conditions during start-up before the steady state conditions
are reached.

2.1.2 Mass Conservation Law

One of the basic laws of physical science is the Law of Conservation of Mass. This
law, stated simply, says that mass cannot be created or destroyed in ordinary chemical
and physical processes. (In the cases of nuclear or atomic reactions the mass does not
conserve and it converts to energy.) Therefore, the total mass of all materials entering any
process plus the mass generated in the system must equal the total mass of all materials

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leaving plus the mass of any materials accumulating in the process. A mass balance for
the system can be written in a general form of
input + generation = output + accumulation
Above equation is known as the general mass-balance equation. The mass in the
equation can be total mass, mass of a particular molecular, or atomic elements. The
accumulation term can be positive or negative. A negative accumulation represents
depletion of pre-existing materials. If there is no generations (no chemical reactions):
input = output + accumulation
In continuous processes of steady state, no accumulation of materials occurs, then
the input will simply equal the output. In other words, what goes in must come out:
input = output (steady state)

2.1.3 Simple Material Balances

In simple material balances at steady state with no chemical reaction, we can use
units of kg, lbm, lbmol, g, kmol, etc. as long as it is consistent. When chemical reactions
involve, kmol or lbmol should be used, since chemical reactions occur stoichiometrically.
To solve a material balance problem, it is advisable to follow some general steps:
1. Sketch a process diagram. This can be a simple box showing each entering
and leaving streams, including any known compositions, amounts,
temperatures, etc.
2. Write the chemical reaction equations involved if any.
3. Select a basis for calculation. In most cases, the specific amount of one of the
streams in the process, either given or to be found, is selected as the basis.
4. Make a material balance using the general mass-balance equation. The
equation can be on the total material balance or on one or each component
present. If chemical reactions involve, use the total mass balance and/or
elements balances.
5. Repeat (3) and (4), if necessary, for multiple unknowns.

Example 3.1: Concentration of sugar beet slurry. A fresh extracted and strained sugar
beet slurry containing 8%wt solids is fed to an evaporator. Water is
removed to increase the solids content to 45%wt. For a feeding stream of
0.3 kg/s, calculate the amounts of (a) water and (b) the concentrated sugar
beet solution.
Solution: Draw a box diagram and list all given information with the entering and
leaving streams. Note that there is no chemical reaction in the system.

Sugar beet slurry Conc. slurry

evaporator X kg/s, 45%
0.30 kg/s, 8%

Water
(0.30 – X) kg/s
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 BE 242 Engineering Analysis & Design

Since the total amounts of water and concentrated slurry streams are
wanted, let x = concentrated slurry (kg/s) and the water removed is then 0.3 – X
(kg/s):
Materials balance on solids: 0.308% = (0.3 – X)0% + X·45%
Therefore, X = 4.00 kg/s or the concentrated slurry is 0.0533 kg/s.
Te water removed is then: 0.30 – X = 0.247 kg/s
As a double check of above calculation, we can write out:
0.30 =?= 0.05333 + 0.257
Result shows that the material balance is correct.

2.1.4 Material Balances and Recycle

To increase the productivity, processes can have a recycle or feedback of part of the
product into the feeding stream. For example, in crystallization of NaCl, part of the
exhaust liquor from the crystallizer is recycled back to the feeding line where it mixes
with fresh salt solution. In some food-drying operations, the humidity of the entering air
is controlled by recirculating part of the hot wet air that leaves the dryer. If chemical
reactions involve and the conversion rate is not 100%, the unreacted materials can be
separated and fed back to the feeding line of the reactor.

Example 3.2: Crystallization of NaCl with recycle. A feed solution of 20%wt NaCl is fed
at 0.50 kg/s to an evaporator, which evaporates some water to concentrate
the NaCl to 48%wt. This concentrated solution is then fed to a crystallizer,
where crystals containing 98%wt NaCl are removed. The saturated
solution containing 38% NaCl is recycled to the evaporator. Calculate the
amount of recycle stream R in kg/s and the product stream of crystals P in
kg/s.
Solution: Figure below shows the process. Choose 0.50 kg/s of fresh feed as basis.
No chemical reactions.
Water, W
juice

Feed 0.5 kg/s S kg/s

Evaporator Crystallizer
20% NaCl 48% NaCl

Recycle, R kg/s Crystal, P kg/s

38% NaCl 98% NaCl

Make an overall balance on the entire process for NaCl and solve for P directly:
0.5020% = W0% + P98% (1)

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P = 0.102 kgcrystals/s (2)

To calculate the recycle stream, we can make a balance on the crystallizer since it
now contains two unknowns, S and R. A total balance:
S = R + 0.102 (3)
A mass balance on the NaCl:
S48% = R38%+ 0.10298% (4)
Solve S and P using Eqs. (3) and (4) simultaneously:
R = 0.510 kg /s (5)
and S = 0.612 kg/s (6)

2.1.5 Material Balances and Chemical Reaction

In chemical reactions with several reactants, the limiting reactant is that it has an
amount less than that necessary to react stoichiometrically with other reactants.
Therefore, the percent completion of a reaction depends on this limiting reactant actually
converted. When chemical reactions involve, the materials entering a process are likely
different from those entering. It is then convenient to make a molar balance on an
individual component such as an element, an ion, or an inert component.

Example 3.3: Continuous acetic acid fermentation. A continuous fermentation process

converts 60%wt ethanol to acetic acid under aerobic conditions by special
bacteria. The production rate is 5 kg/h acetic acid. The process would be
inhibited if the acetic acid concentration were 12% or higher.
(a) the amount of ethanol required
(b) the amount of water needed to dilute the ethanol to avoid acid
inhibition

Solution: The process is illustrated below.

Vent

EtOH soln.
X kg/h, 30%wt
Fermentation HAc
Unit 5 kg/h, 12%
water
W kg/h

Air

The reaction: C2H5OH + O2  CH3OOH + H2O

(ethanol) (acetic acid)

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(a). Assume no ethanol loss from vent, then:

1 kmol of HAc needs 1 kmol of EtOH. The molecular weights of EtOH and
HAc are 46 kg/kmol and 60 kg/kmol, respectively. therefore,
 the 30% ethanol needed:
X = [(5kg/h)/(60 kg/kmol)46 kg/kmol ]/60% = 6.39 (kg/h)

(b). material balance on water, assuming no water loss from vent:

water in ethanol solution + water stream = water in HAc solution
6.39(1 – 30%) + W = 5(1 – 12%)
 W = 1.84 kg/h

2.1.6 Material Balances and Fuel Combustion

Combustion is one type of chemical reaction. Basic equations for combustion and
the heat of formation of the combustion products (at 298K) include:
1). H2 + ½ O2  H2O (g) hf = - 241.81 kJ/mol
H2 + ½ O2  H2O (l) hf = - 283.99 kJ/mol
2). C + ½ O2  CO (g) hf = - 110.53 kJ/mol
3). C + O2  CO2 (g) hf = - 393.51 kJ/mol
4). S + O2  SO2 (g) hf = - 296.84 kJ/mol

Air Properties:
Molar or volume ratio: O2:N2 = 1: 3.76; Air:N2 = 1.26:1
Mass ratio: O2:N2 = 1: 3.32; Air:N2 = 1.31:1
Composition (%v or %mol): O2 – 21%, N2 – 79%
Composition (%wt): O2 – 23.3%, N2 – 76.7%
Molecular weight: 28.8 kg/kmol

Theoretical Oxygen Needed for a Fuel:

If a fuel has the formula:

CxHyOzSw + (4x + y -2 z + 4w)/4 O2  xCO2 + y/2 H2O + wSO2

The amount of theoretical oxygen (kmol/kg) is calculated by:

%C % H %O %S
kmolO / kg fuel    
2
12 4 32 32

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The volume of theoretical oxygen (101kPa and 298K) is calculated by:

 %C % H %O % S 
m 3 O2 / kg fuel  24.45    
 12 4 32 32 

where: %C, %H, %O and %S are the decimal weights of the elements of
carbon, hydrogen, oxygen, and sulfur, respectively, in the fuel.

Excess Air
The amount of excess air for combustion can be calculated from a dry analysis of
the products of combustion. The percent excess air, Ax, is calculated using the following
equation, which assumes there is a negligible amount of nitrogen in the fuel:
AExcess air (kmol) Aactual  ATheoretical  A 
Ax %  100%  100%   actual  1 100%
ATheoretical (kmol) ATheoretical  Theoretical
A 
If combustible gases (e.g., CO or H2) are present in the products of combustion, the
percent excess air is calculated from the Orsat formula:
%O2  0.5(%CO  % H 2 )
Ax   100%
0.266  % N 2  %O2  0.5(%CO  % H 2 )

where: %O2, %N2 , %CO, and %H2 are the molar or volume percentage of oxygen,
nitrogen, carbon monoxide, and hydrogen, respectively, in the flue gas. If fuel contains
oxygen, its contribution to the oxygen percentage in the flue gas should be subtracted.
There are three types of combustion problems: (1) the composition of the fuel is
given, find the oxygen (or air) required to obtain a given flue gas composition; (2) given
the amount of air used and the fuel composition, find the composition of the flue gas;
and (3) the flue gas composition is given, find the fuel composition. If a solid (e.g., coal) is
in the fuel, the amount of ash will also be given. Either the total fuel mass or the carbon
mass will be the tie element in this type of problem. Use the following steps when
solving combustion problems:
Step 1: Break the fuel into its basic elements on mole basis (C, O2, N2, H2, S).
Step 2: Equate the quantities of carbon in the flue gas and fuel.
Step 3: Determine the air requirements from a nitrogen balance.
Step 4: Determine the excess air from an oxygen balance
Step 5: Determine the moisture content using a hydrogen balance.

Example 3.4: Combustion of Fuel. The elemental composition of a liquid fuel contains
9.3%wt hydrogen, 88.7%wt of carbon, and 2.0%wt of oxygen. The flue gas
composition (%mol) is 1% H2, 1.5% CO, 14.0% CO2, 2.5% O2, and 81% N2. The
average molecular weight is 120 kg/kmol. For 100 kmol of flue gas, calculate
a). the amount of fuel supplied (kmol)
b). the theoretical amount of air ( in m3 at 273.15K and 101.325kPa) needed
c). the percentage of excess air

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Solution: Draw a process flow diagram including the compositions of feed and flue gas.

Supply air, A (kmol) Flue gas, 100 kmol

Combustion
1.0 kmol H2
Liquid fuel, F (kmol) Chamber
1.5 kmol CO
9.3%wt H 14.0 kmol CO2
88.7%wt C 2.5 kmol O2
2.0 %wt O 81.0 kmol N2

(a). Solving for the amount of fuel supplied. Based on carbon balance:
The chemical reactions of carbon are:
C + ½ O2—CO (1)
C + O2 — CO2 (2)
And total carbon in the feed = total carbon in the flue gas
Carbon in the flue gas (kmol):
 Fcarbon = 1.5 (from CO) + 14 (from CO2) = 15.5 (kmol)
Since the atomic weight of carbon is 12 kg/kmol:
 Fcarbon = 15.512 = 186 (kg)
Since carbon is 88.7%wt of the fuel:
 Ffuel = Fcarbon /88.7% = 186/88.7% = 209.7 (kg)

Since the molecular weight of the fuel is 120 kg/kmol

 Ffuel = 209.7 /120 = 1.747 (kmol)

(b). Solving for the theoretical amount of air: From eqs. (1) & (2) above, the
oxygen needed for burning the carbon is
 FO2, C = 1.5/2 (from CO) + 14 (from CO2) = 14.75 (kmol)

The total elemental hydrogen in the feed for 100 kmol of flue gas:
FH,total = Ffuel 9.3% = 209.79.3% = 19.5 (kg) = 19.5 (kmol)
But 1 kmol is left unburned in flue gas. Based on the chemical reaction,
H + ¼ O2 — ½ H2O (3)
the oxygen needed for complete combustion of hydrogen:
FO2,H = (19.50 – 1)/4 = 4.625 (kmol)
Recall that there is 2%wt oxygen in the fuel which could theoretically be
used for combustion. Therefore, the theoretical O2 needed:
FO2, theo. = FO2, C + FO2,H - FO2,F
= 14.75 + 4.625 – (209.72%/32) = 19.244 (kmol)

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Air composition can be assumed as 21%mol of O2 and 79%mol of N2, so the

theoretical air needed:
Atheo. = 19.244/21% = 91.64 (kmol)

At 273.15K and 101.325kPa , 1 kmol ideal gas = 22.4 m3. Assume air is an
ideal gas, then the theoretical air needed in m3 is
Athoe. = 91.6422.4 = 2,053 (m3)

(c). Solving for the percentage of excess air. The % excess air is defined as

Aexcess  A 
Ax %  100%   actual  1 100%
ATheoretical  Theoretical
A 
The theoretical air is calculated above as Atheo. = 91.64 (kmol)
Since no nitrogen is from fuel, the 81%, or 81 kmol, of nitrogen in the flue gas
is assume all from the air supplied. Since FN2 = 81 kmol, then the actual air
Aactual = FN2 / 79% = 81 / 79% = 102.53 kmol
Therefore the access air percentage is
 102.53 
Ax %    1  100% = 11.88%
 91.64 

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2.1.7 Unsteady State Material Balances

Time involves when a process is transit. Differential equations are needed in this
type of material balances.

Example 3.5: Preparation of salt solution. Water (150kg/h) and salt (30kg/h) are added
into a mixing tank. Assuming complete mixing, the salt concentration is
uniform in the tank. The solution flows out of the tank at a rate of 120
kg/h. Before salt is added, the tank has 100 kg fresh water in it. Calculate
(1) the total mass of solution in the tank after one hour, and (2) the salt
concentration that flows out of tank after one hour.
Solution:
Let wA = mass flow rate of water, kg/h
Water (A) Salt (B)
wB = mass flow rate of salt, kg/h
wC = mass flow rate of solution, kg/h 150kg/h 30kg/h

M = solution accumulated in the tank, kg

t = time, h
aA = salt concentration of stream A, kg/kg Salt Solution (C)
aB = salt concentration of stream B, kg/ kg 120kg/h
aC = salt concentration of stream C, kg/ kg

(1). Overall mass balance:

wAdt + wBdt = dM + wCdt (1)

Rearrange Eq. (1):

150 + 30 = dM + 120 (2)
dt

 dM = 60 (3)
dt
Therefore, after integration:
M = 60t + 100 (M0 = 100 kg) (4)
When t = 1 h,
M1 = 601 + 100 = 160 (kg) (5)

(2). Mass balance on salt:

wAaAdt + wBaBdt = d(MaC) + wCaCdt (6)
(note: salt concentration in the tank = salt concentration in stream C)

Rearrange Eq (2):
d ( M  ac )
wAaA + wBaB = + wCaC` (7)
dt
Expend the differentiation term:

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dac dM
wAaA + wBaB = ( M  ac )+ wCaC` (8)
dt dt
Substitute the following:
wA = 150, wB = 30, wC = 120, aA = 0, aB = 1, dM = 60, and M = 60t + 100
dt
dac
1200 +30×1.0 = [(60t + 100) + 60aC] + 120aC (9)
dt
Rearrange:
dt dac (10)

60t  100 30  180a c

t ac
Integration dt dac (11)

 60t  100  30  180a
0 0 c

a
or 1 t d ( 60t  100 ) 1 c d ( 30  180ac ) (12)
  
60 0 60t  100 180 0 30  180ac

1  60  t  100  1  30  180  a C  (13)

 ln   ln 
60  100  180  30 

1   10 
3
gives ac  1     (14)
6   6t  10  


1   10  
3
when t = 1 (h): ac  1      0.126 (15)
6   6  10  
 

2.1.8 Exercises of Material Balances

Ex.1 Processing of Fish Meal. Fish are processed into fish meal as a supplementary
protein food. In the processing the oil is first extracted to produce wet fish cake
containing 80%wt water and 20%wt bone-dry cake. This wet cake feed is dried in
rotary drum dryers to give a “dry” fish cake product containing 40 %wt water.
Finally, the product is finely ground and packed. Calculate the kg/h of wet cake
feed needed to produce 1000kg/h of “dry” fish cake product.
Ex. 2 Continuous filtration. A fermentation broth contains 6%wt of cell solids and
0.05%wt protein. The biomass is filtered using a continuous rotary vacuum filter.
To improve filtration rates, a filter aid is added at a rate of 10 kg/h. Liquid filtrate
is collected at 95 kg/h. The concentration of protein in the filtrate is 0.045%wt.
Filter cake containing cells and filter aid is continuously removed from the filter
cloth. If 120 kg/h fermentation broth is fed to the filter,
(a) How much liquid (%wt) remains the filter cake?
(b) How much protein is absorbed per kg filter aid (kg/kg)?

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Ex. 3 In a wood drier the hot air must contain at least 3%wt water to prevent the wood
from drying too rapidly to split or warp. The original fresh air contains 1%wt
water. Wood is dried from 35%wt water to 12 %wt water. The wet air leaving the
drier contains 8%wt water. Calculate the amount of wet air that must be returned
to the drier if one ton per hour (2000 lb/h) of wet wood is dried.
Recycle

Drying air
Makeup Air 3% Moisture Splitter Exhaust Air
Mixer
1%wt moisture 8%wt moisture
Wet wood
Dryer
2000 lb/h Dry wood
35%wt moisture 12%wt
moisture

Ex. 4 Combustion. Given the flue gas composition per 100 kmol of dry flue gas,
determine (a) the amount of fuel burned (kg), (b) the amount of air used (m3 at
STP), and (c) the excess air used (%). The fuel has a molecular formula of C 6H12O.
Component Composition (%mol)
CO2 11.0%
O2 6.4%
N2 82.6%

Ex. 5 Non-steady state problem. In a food processing plant, canola oil is used for
preparing breadcrumbs. The stirred buffering oil tank has a maximum capacity of
800 L and usually holds 500 L of working volume. During normal operations, the
oil is pumped out at a rate of 40 L/h. One day during a night shift, the oil tank is
mistakenly connected to a drum of cod-liver oil which is then pumped into the
tank. The mixed oil is also continuously pumped out at 40 L/h. Assume the
densities of the oils are the same.
(a). If the cod-liver oil is pumped in at a rate of 40 L/h, what is the composition
of the oil mixture in the tank when morning shift workers arrive? (One shift
is 8 hours)
(b). If the flow rate of cod-liver oil is 70 L/h instead of 40 L/h, will the tank
overflow before the morning shift workers arrive? What is the cod-liver oil
concentration by that time?

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2.2 Energy Conservation and Heat Balances

2.2.1 Conservation of Energy

In making material balances, we used the law of conservation of mass, which states
that the mass entering a system is equal to the mass leaving the system plus
accumulation in the system. Similarly, the law of conservation of energy says that all energy
entering a system is equal to that leaving plus accumulation in the system.

2.2.2 Energy Forms

Energy can appear in many forms. Some of the common forms are enthalpy,
electrical energy, chemical energy (in terms of enthalpy of reaction), kinetic energy,
potential energy, work, and heat.
Pressure energy: p· v (v: m3/kg, p: Pa)
Potential energy: m·z·g (m: kg, z: m, g = 9.81 m/s2 )
Kinetic energy: m·v2/2 (m: kg, v: m/s)
Internal energy: m·u (m: kg, : u: J/kg)
Work or Heat is the energy in transit and could not be stored. Two common types
of work are mechanical work and electrical work. Heat is energy in transit as a result of a
temperature change. Other forms of energy, i.e., surface energy, magnetic energy, and
electrostatic energy, are of lesser importance in the biological and agricultural
engineering fields.

2.2.3 Energy Balance

If a system does an amount of work, W, on its surroundings and receives an
amount of heat, Q, from its surroundings, the total energy change, E, is then:
E = Q - W
The W and Q are algebraically positive by definition. If the system is done a work
by its surroundings, or it gives heat out to its surroundings, the value of W or Q becomes
negative. If the system has chemical reactions that give off heat, then Q is negative.
Total energy change is the changes of all four forms of energy: m·p·v, m·z·g,
m·v2/2, and m·u:
E = ( m·p·v + m·z·g + m·v2/2 + mu)
= m·(p·v) + m·(z·g) + m·(v2/2) + m·u
= m·{(p·v) + (z·g) + (v2/2) + u}
where: (p·v) = p2·v2 – p1·v1 (z·g) = (z2 – z1) g
(v2/2) = (v22 – v12)/2 u = u2 – u1
Therefore, the overall energy change of a system can be expressed by:
Q - W = m·{(p·v) + (z·g) + (v2/2) + u}

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2.2.4 Sensible Heat and Latent Heat

Sensible heat is the heat transferred due to a temperature change, Qs = m·Cp·T.
Latent heat is the heat transferred due to phase change at constant temperatures, which
includes:
1). heat of fusion is the heat for melting a unit of a solid
2). heat of vaporization is the heat for vaporizing a unit of liquid
3). heat of sublimation is the heat for vaporizing a solid without undergoing through
a liquid phase
4). heat of transition is the heat involved when one solid phase changes to
another solid phase

2.2.5 Enthalpy
Enthalpy is a thermodynamic property of a system. It is the sum of internal energy
and the product of pressure and volume. It is also known as the total heat and heat
content in a system. Enthalpy is defined as follows
H = E + PV
We cannot measure the absolute values of enthalpy, but we can look at changes in
enthalpy by choosing a reference (usually 25ºC and 101.325kPa).
H = E + PV
If pressure is constant:
H = E + PV
The change in enthalpy, H, is equal to the change in internal energy, E, plus PV
work, PV.
The enthalpy, H, of a substance in kJ/kg represents the sum of the internal energy
plus the pressure-volume term. Enthalpy is a state property. It is the function of the end
states of a system and independent of processes. For no reaction and a constant-pressure
process with a change in temperature, the heat change is the difference in enthalpy, H,
of the substance relative to a given temperature or base point.

2.2.6 Specific Heat Capacity

Specific heat capacity is the proportional coefficient of the internal energy change
due to random motion of atoms in a sample as a function of temperature, normalized by
dividing by the mass of the sample. Because the internal energy is normally linear versus
temperature change, it can be approximated by measuring the heat required to raise the
temperature of 1 kg of a substance by 1 °C or one Kelvin. This can be stated by the
following equation:
Qs = m·Cp·T
Where Cp is the specific heat capacity in the unit of kJ/kg·K in SI unit and Btu/lbm·R in

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English unit (1 Btu/lbm·R = 4.1868 kJ/kg·K). The relationship does not apply if a phase
change is encountered, because the heat added or removed during a phase change does
not change the temperature. Heat capacity is a property of a substance. If a substance has
stronger intermolecular forces such as hydrogen bonding in water, it is likely to have a
higher heat capacity. Heat capacity is a function of temperature. For example, the heat
capacity of water at 25ºC is different from that at 100 °C. Usually a quadratic relationship
is used to correlate the function of temperature:
Cp = a + bT + cT2
The total heat change can be calculated by
T2
Qs  m   C p (T )  dT = m(aT + bT2/2 + cT3/3)
T1

If the range of temperature change is small, an average constant Cp can be

assumed. The heat capacities of gases (sometimes called specific heat) at constant
pressure Cp are functions of temperature too and for most engineering purposes can be
assumed independent of pressure up to several atmospheres. In most engineering
calculations, one is usually interested in the amount of heat needed to heat a gas from
one temperature T1 to another at T2, an integration must be performed or a suitable mean
Cpm be used.
The heat capacities of water and air under constant pressure and 25ºC are 4.184
kJ/kg·K and 1.0048 kJ/kg·K, respectively.
In calculating the heat exchanged due to temperature changes in heat exchangers,
the following relationship can be applied:
|Qs, hot fluid |= |Qs, cold fluid | + |Q loss |

Example 3.2.1: Heating of milk. Rich cows’ milk (4536 kg/h) at 4.4°C is being heated in
a heat exchanger to 54.4°C by hot water. How much heat is needed? The
average heat capacity of rich cows’ milk is 3.85 kJ/kg K.
(This example is adapted from Example 1.6-2 in: Christie J. Geankoplis, Transport Processes
and Unit Operations, 3rd ed. Printice Hall, New Jersey, 1993)

Solution: 4536 kg/h = 1.26 kg/s

 heat required Q s = m·Cp·T = 1.26  3.85  (54.4 – 4.4 ) = 242.5 kW

Example 3.2.2: Heating of N2 Gas. The gas N2 at 1 atm pressure absolute is being heated
in a heat exchanger. Calculate the amount of heat needed in kJ to heat 3.0
kg N2 in the following temperatures:
(a). 298K to 673 K (Cpm = 1.06 kJ/kg·K)
(b). 298K to 1123 K (Cpm = 1.11 kJ/kg·K), and
(c). 673K to 1123 K
(This example is adapted from Example 1.6-1 in: Christie J. Geankoplis, Transport Processes
and Unit Operations, 3rd ed. Printice Hall, New Jersey, 1993)

Solution: For case (a), Cpm = 1.06 kJ/kg·K which is the mean heat capacity for the
range of 298—673 K. Therefore, the heat required = m·Cpm ·(T2 – T1)

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 BE 242 Engineering Analysis & Design

Substituting the known values:

heat required Qs = (3.01.06)(673 - 298) = 1.19 (kJ)

For case (b), Cpm = 1.11 kJ/kg·K.

heat required Qs= 3.01.11(1123 - 298) = 2.74 kJ

For case (c), there is no mean heat capacity for the interval 673—1123 K. However, we can
use the heat required to heat the gas from 298 to 673 K in case (a) and subtract it from
case (b), which includes the heat to go from 298 to673Kplus 673to 1123K, i.e.,
heat required (673~1123 K) = heat required (298~1123 K) - heat required (298~673)
Substituting the proper values into above equation:
Heat required Q s = 2.74 – 1.19 = 1.55 kJ

When heating a gas mixture, the total heat required is determined by first
calculating the heat required for each individual component and then adding the results
to obtain the total.

Example 3.2.3: Non-constant Cp example. Water passing through a heat exchanger is

heated from 4°C to 100°C. The specific heat capacity (in kJ/kgK) of the
liquid is a function of temperature: Cp = 8×10-5T2 - 3×10-3T + 4.219. Where
T is temperature in °C. How much heat does the water gain through the
heat exchanger if the flow rate is 1.5 kg/s?
Solution: Since Cp is a function of temperature, integration is needed to calculate
the heat exchange, or:
T2 T2
Qs   mC p dT  m  C p dT
T1 T1

Qs  m  8  105 T 2  3  103 T  4.219dT

T2

4
100
 8  105 3 3  103 2 
 m T  T  4.219  T 
 3 2 4
 8  105 3  103  
  1003   1002  4.219  100 
  3 2  
 1.5 
  8  105 3  10 3
 
    43   4 2  4.219  4 
  3 2 
= 625.1 (kJ/s)

Therefore, the total heat transfer rate is 625.1 kJ/s or 625.1 kW.

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BE 242 Engineering Analysis & Design

2.2.7 Steam Table

Since water is a very common chemical, the thermodynamic properties of water
have been compiled in steam tables. Steam tables list the thermodynamic properties of
water, including specific volume, internal energy, and enthalpy. Enthalpies are the main
interests in heat balance. All enthalpy values must have a reference point. In most steam
tables the triple point, 0.01°C and 0.6112 kPa at which ice, liquid water and water vapor
are in equilibrium and co-exist, is used as the reference point, or Hliquid = 0. Steam tables
eliminate the need for sensible-heat and latent-heat calculations for water and steam, and
can be used directly in heat balance calculations.
Saturated liquid and vapor are in equilibrium with each other. For water, once the
temperature is specified, saturation occurs at only one pressure. For example, saturated
steam at 150°C has a pressure of 475.8 kPa, the enthalpy of this steam is 2746.5 kJ/kg
relative to the triple point of water, and the corresponding liquid water has an enthalpy
of 632.20 kJ/kg. The heat of vaporization under these conditions is the difference between
liquid and vapor enthalpies, which is 2114.3 kJ/kg.
The effect of pressure on enthalpy of liquid water is minor and usually neglected in
steam tables. For example, the enthalpy of water at 25°C and 101kPa is found by looking
up the enthalpy of saturated water at 25°C in steam table, and assuming it is independent
of pressure. This assumption is valid if the pressure is less than 5 MPa.
If the temperature of saturated vapor is increased or the pressure decreased at
constant temperature, the vapor is superheated. A superheated vapor cannot condense
until it is returned to saturation conditions. The difference between the temperature of a
superheated gas and its saturation temperature is called the degrees of superheat. Steam
tables are tabulated either by temperatures or by pressures. Tables of superheated steam
are also included in some reference books.
A steam table is tabulated by temperature in SI units on next page.
The equation for computing the energy change involving phase change, e.g., from
steam to liquid water, is as below:
Q = H = m·(h2 – h1) = m·h
Where h2 and h1 are the specific enthalpies of the system at ending state and starting
state, respectively, and Q is typically in kJ/kg
In the hot source is steam, to calculate the heat exchanged in heat exchangers, the
following relationship can be applied:
|Qst, hot fluid |= |Qs, cold fluid | + |Q loss |
Please note that the above equation can be used to calculate the sensible heat
change also, as long as the specific enthalpies are of the state points are known.

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 BE 242 Engineering Analysis & Design

Properties of Saturated Steam and Water

Vapor Specific Volume Specific Enthalpy Specific Entropy
Temp.
Pressure (m3/kg) (kJ/kg) (kJ/kg)
(°C) (kPa) Liquid Sat’d vapor Liquid Sat’d Vapor Liquid Sat’d Vapor
0.01 0.6113 0.0010002 206.1 0.000 2501.4 0.0000 9.1562
3 0.7577 0.0010001 168.1 12.57 2506.9 0.0457 9.0773
6 0.9349 0.0010001 137.7 25.20 2512.4 0.0912 9.0003
10 1.228 0.0010004 106.4 42.01 2519.8 0.1510 8.9008
12 1.402 0.0010005 93.78 50.41 2523.4 0.1806 8.8524
15 1.705 0.0010009 77.93 62.99 2528.9 0.2245 8.7814
18 2.064 0.0010014 65.04 75.58 2534.4 0.2679 8.7123
20 2.339 0.0010018 57.79 83.96 2538.1 0.2996 8.6672
22 2.645 0.0010022 51.45 92.33 2541.7 0.3251 8.6229
25 3.169 0.0010029 43.36 104.9 2547.2 0.3674 8.5580
27 3.567 0.0010035 38.77 113.3 2550.8 0.3954 8.5156
30 4.246 0.0010043 32.89 125.8 2556.3 0.4369 8.4533
33 5.034 0.0010053 28.01 138.3 2561.7 0.4781 8.3927
35 5.628 0.0010060 25.22 146.7 2565.3 0.5053 8.3531
40 7.384 0.0010078 19.52 167.6 2574.3 0.5725 8.2570
45 9.593 0.0010099 15.26 188.5 2583.2 0.6387 8.1648
50 12.35 0.0010121 12.03 209.3 2592.1 0.7038 8.0763
55 15.76 0.0010146 9.568 230.2 2600.9 0.7679 7.9913
60 19.94 0.0010172 7.671 251.1 2609.6 0.8312 7.9096
65 25.03 0.0010199 6.197 272.1 2618.3 0.8935 7.8310
70 31.19 0.0010228 5.042 293.0 2626.8 0.9549 7.7553
75 38.58 0.0010259 4.131 313.9 2635.3 1.0155 7.6824
80 47.39 0.0010291 3.407 334.9 2643.7 1.0753 7.6122
85 57.83 0.0010325 2.828 355.9 2651.9 1.1343 7.5445
90 70.14 0.0010360 2.361 376.9 2660.1 1.1925 7.4791
95 84.55 0.0010397 1.982 398.0 2668.1 1.2500 7.4159
100 101.4 0.0010435 1.673 419.0 2676.1 1.3069 7.3549
105 120.8 0.0010475 1.419 440.2 2683.8 1.3630 7.2958
110 143.3 0.0010516 1.210 461.3 2691.5 1.4185 7.2387
115 169.1 0.0010559 1.037 482.5 2699.0 1.4734 7.1833
120 198.5 0.0010603 0.8919 503.7 2706.3 1.5276 7.1296
125 232.1 0.0010649 0.7706 525.0 2713.5 1.5813 7.0775
130 270.1 0.0010697 0.6685 546.3 2720.5 1.6344 7.0269
135 313.0 0.0010746 0.5822 567.7 2727.3 1.6870 6.9777
140 316.3 0.0010797 0.5089 589.1 2733.9 1.7391 6.9299
145 415.4 0.0010850 0.4463 610.6 2740.3 1.7907 6.8833
150 475.8 0.0010905 0.3928 632.2 2746.5 1.8418 6.8379
155 543.1 0.0010961 0.3468 653.8 2752.4 1.8925 6.7935
160 617.8 0.0011020 0.3071 675.5 2758.1 1.9427 6.7502
165 700.5 0.0011080 0.2727 697.3 2763.5 1.9925 6.7078
170 791.7 0.0011143 0.2428 719.2 2768.7 2.0419 6.6663
175 892.0 0.0011207 0.2168 741.2 2773.6 2.0909 6.6256
180 1002 0.0011274 0.1941 763.2 2778.2 2.1396 6.5857
190 1254 0.0011414 0.1565 807.6 2786.4 2.2359 6.5079
200 1554 0.0011565 0.1274 852.4 2793.2 2.3309 6.4323
225 2548 0.0011992 0.0785 966.8 2803.3 2.5639 6.2503
250 3973 0.0012512 0.0501 1085.4 2801.5 2.7927 6.0730
275 5942 0.0013168 0.0328 1210.1 2785.0 3.0208 5.8938
300 8581 0.0010436 0.0217 1344.0 2749.0 3.2534 5.7045

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BE 242 Engineering Analysis & Design

Example 3.2.4: Use of steam table. Find the enthalpy change (i.e., how much heat must
be added) for each of the following cases.
(a) Heating 1 kg water from 21°C to 60°Cat 101.325 kPa pressure.
(b) Heating 1 kg water from 21 ºC to 115°C and vaporizing at 169.06 kPa.
(c) Vaporizing 1 kg water at 115 °C and 169.06 kPa.
(This example is adapted from Example 1.6-3 in: Christie J. Geankoplis, Transport
Processes and Unit Operations, 3rd ed. Printice Hall, New Jersey, 1993)

Solution: (a). the effect of pressure on the enthalpy of liquid water is negligible. From
steam table,
The H of Liquid water at 21º C h1 = 88.14 kJ/kg
The H of Liquid water at 60 ºC h2 = 251.13 kJ/kg
The change in H: H = m·(h2 – h1) = 1x(251.13 - 88.14) = 162.99 kJ/kg
(b) Enthalpy of liquid water at 21º C h1 = 88.14 kJ/kg and the enthalpy at 115°C &
169.06 kPa of the saturated vapor is h2 = 2699.0 kJ/kg:
The change in H: H = m·(h2 – h1) = 1x(2699.0 - 88.14) = 2610.9 kJ/kg
(c). The latent heat of water at 115°C is the difference of saturate liquid water
and saturate water vapor. The H of liquid water at 115 ºC h1 = 482.48
kJ/kg, and the enthalpy at 115°C & 169.06 kPa of the saturated vapor is h2
= 2699.0 kJ/kg. Therefore,
The change in H: H = m·(h2 – h1) = 1x(2699.0 - 484.48) = 2216.52 kJ/kg

2.2.8 Heat of Reaction

When chemical reactions occur, heat effects always accompany these reactions. If
heat is given off, the reaction is exothermic; if heat is absorbed, the reaction is an
endothermic. This heat of reaction is dependent on the chemical properties of each of the
reactants and products.
A standard heat of reaction H° is defined as the change in enthalpy when 1 kmol
reacts under 298.15K and 101.325, or H° is in kJ/kmol. For example, for the reaction
C(s) + ½ O2 (g) — CO (g) H°R = -110.5103 kJ/kmol
C6H12O6 (s) + 6 O2 (g) — 6CO2 (g) + 6H2O (l) H°R = -2,816103 kJ/kmol
(glucose)
The negative sign means the reaction loses enthalpy thus is exothermic. When the
product is formed from reacting elements, the heat of reaction H°R is given a special
name heat of formation, Hºf , such as when CO is formed from C and O2. If a chemical
reaction is combustion and CO/CO2 and H2O are formed in the reaction, the heat of
reaction is also called heat of combustion, Hºc . Data of Hºf and Hºc are usually given in
various chemistry and other handbooks.
If the data of heat of formation are available, the standard heat of the reaction,
H°R, in kJ/kmol, can be calculated by
H°R =  (niHºf, i) products -  (mjHºf, j) reactants
Where: ni and mj are the coefficients of product i and reactant j, respectively, in the
balanced chemical reactions.

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 BE 242 Engineering Analysis & Design

Example 3.2.5: Combustion of carbon. A total of 10.0 kmol of carbon graphite is burned
in a calorimeter held at 298 K and 1 atm. The combustion is incomplete
and 90% of the C goes to CO2 and 10% to CO. What is the total enthalpy
change in kJ ? Given: Hºc for carbon going to CO2 is -393.513103
kJ/kmol, and for carbon going to CO is -110.523 103 kJ/kmol.
(This example is adapted from Example 1.6-4 in: Christie J. Geankoplis, Transport
Processes and Unit Operations, 3rd ed. Printice Hall, New Jersey, 1993)

Solution: the reactions are as follows:

C(s) + O2 (g) — CO2 (g) Hºc = -393.513103 kJ/kmol
C(s) + ½ O2 (g) — CO (g) Hºc = -110.523 103 kJ/kmol

Since 9 kmol CO2 and 1 kmol CO are formed

 HoR = 9(-393.513103) + 1(-110.523103) = -3,652103 (kJ)

Example 3.2.6: Reaction of methane reforming. For the following reaction of 1 kmol of
CH4 at 101.32 kPa and 298 K,
CH4 (g) + H2O (l) — CO (g) + 3H2 (g)
calculate the standard heat of reaction H°R at 298 K in kJ.
(This example is adapted from Example 1.6-3 in: Christie J. Geankoplis, Transport
Processes and Unit Operations, 3rd ed. Printice Hall, New Jersey, 1993)

Solution: the standard heats of formation at 298 K:

Hºf (kJ/kmol)
CH4 (g) -74.848 103
H2O (l) -285.840 103
CO (g) -110.523 103
H2 (g) 0

Note that the Hºf of all elements is, by definition, zero.

Since H°R =  (niHºf, i) products -  (mjHºf, j) reactants
 H°R = [1x(-110.523 103) + 3x(0)]
– [1x(-74.848 103) + 1x(-285.840 103)]
= + 250.165 103 kJ/kmol (endothermic)

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BE 242 Engineering Analysis & Design

2.2.9 Heat Balance

In many cases of process engineering, which often takes place at constant pressure,
electrical energy, kinetic energy, potential energy, and work either are not present or can
be neglected. Then only the enthalpy of the materials (at constant pressure), the standard
chemical reaction energy (H°), and the heat added or removed must be taken into
account in the energy balance. This is generally called a heat balance.
In making a heat balance at steady state we use methods similar to those used in
making a material balance. The energy or heat entering a process in the inlet materials
plus any net energy added to the process is equal to the energy leaving in the materials.
Mathematically,
(HR) + (-Hº298) + q = (Hp)
where (Hr) is the sum of enthalpies of all materials entering the reaction process
relative to the reference state for the standard heat of reaction at 298 K and 101.32 kPa. If
the inlet temperature is above 298 K, this sum will be positive. Hº298 is the standard heat
of the reaction at 298 K and 101.32 kPa. The reaction contributes heat to the process, so
the negative of Hº298 is taken to be positive input heat for an exothermic reaction. q is the
net energy or heat added to the system. If heat leaves the system, this item will be
negative. (Hp) is the sum of enthalpies of all leaving materials referred to the standard
reference state at 298 K.
Many of the points described for material balances also apply to energy balance:
(i) Draw and label a flow diagram to identify all inlet and outlet streams and their
compositions. For energy balances, the temperatures and phases of the
material should also be indicated if appropriate
(ii) State clearly the units selected for the energy balance and label them in the
flow diagram
(iii) Choose a basis for the calculation
(iv) Choose the reference state for H = 0. Without chemical reactions, the reference
states could be arbitrarily assigned, sometime even without explicit description
since in most cases the change of the enthalpy is the concern, not the absolute
values.
(v) State all assumptions used such as no heat loss if the system is well insolated,
negligible heats of mixing, no liquid loss through evaporation if a component
is not particularly volatile or if the temperature is relatively low, etc.

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 BE 242 Engineering Analysis & Design

Example 3.2.6: Heating of Fermentation broth. A liquid fermentation medium at 20°C is

pumped at a rate of 0.55 kg/s through a heat exchanger, where it is
heated to 37°C under pressure. The water used to heat the broth enters at
75°C and leaves at 60°C. The average heat capacity of the fermentation
medium is 4.10 kJ/kg·K, and that for water is 4.14 kJ/kg·K. Calculate the
water flow rate and the heat added to the fermentation broth. Assume no
heat losses.
Solution: The process flow is given in figure below. Use 273.15K or 0ºC as the reference
state to calculate the various enthalpies.

Liquid Liquid
0.55 kg/s, 20ºC 0.55 kg/s, 37ºC
Heat Exchanger
Unit
Water Water
W kg/s, 75ºC
W kg/s, 60ºC

No chemical reaction and no heat losses or additions:

Heat input: HR of the enthalpies of the two streams relative to 273.15 K (0°C)
Hliquid = (0.55 kg/s)(4.10 kJ/kg K)[(20 +273.15K) – 273.15]
= 45.1 kJ/s
Hwater = W(4.14)[(75 +273.15 25) – 273.15] = 310.5 W kJ/s

Heat output: Hp of the two streams relative to 273.15K(0°C):

Hliquid = 0.554.10[(37 + 273.15) – 273.15] = 83.4 (kJ/s)
Hwater = W4.14[(60 + 273.155) – 273.15] = 248.4W (kJ/s)
Therefore,
45.1 + 310.5W = 83.4 + 248.4W
 W = 0.617 kg/s water flow

Note in this example that since the heat capacities were assumed constant a
simpler balance could have been written as follows heat gained by liquid = heat lost by
water:
0.55(4.10)(37 — 20) = W·4.14(75 — 60)
Then, solving, W = 0.617 kg/s. This simple balance works well when Cp is constant.
However, when the Cp varies with temperature, integration is needed:
T2
Q   C p (T )  dT
T1

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BE 242 Engineering Analysis & Design

2.2.10 Exercises of Heat Balance

Exercise 1. Heat exchanger. Hot water enters a counter-flow heat exchanger at 60ºC
and 15,000 kg/h. It is cooled to 40ºC by a cold stream of water which
enters at 20ºC and 20,000 kg/h. Determine the exit temperatures of the
cold water when: (1) no heat loss and (2) at heat loss of 50kW. C p = 4.18
kJ/kg·K.

Exercise 2. Steam Table. Determine enthalpy changes for 5 kg water for the
following cases.
(a) Cooling and condensing a saturated vapor at 115°C and 169 kPa abs
to a liquid at 60°C.
(b) Heating liquid water from 20ºC to 105°C and vaporizing at 105°C to
saturate vapor.
(c) Heating liquid water from 25°C to 150°C under pressure.
(d) Condensing a saturated vapor at 180°C and 1002 kPa abs.

Exercise 3. Food sterilization. A canned food needs to be heated to 87ºC for the
purpose of sterilization. Heat capacities of the food vs temperature are
listed in the table below. Saturate steam of 120ºC is used for heating and
leaves the system at 95ºC as liquid water.
T (ºC) Cp (kJ/kg·K)
20 4.019
50 3.905
90 3.726
Find:
(a). how much heat is needed to heat 100 kg of the canned food at 20ºC to
the desired sterilization temperature?
(b). how much steam is needed?

Exercise 4. Combustion of Ethanol. For 100 kg of ethanol, calculate the total heat of
combustion at 298 K and 101.32 kPa, assuming that combustion is
complete and product water is in vapor state.

Hf (kJ/kmol)
Compound
at 298 K and 101.32 kPa
C2H5OH -234.95103
O2 0
CO2 -393.513103
H2O (g) -241.826103

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