THE ENERGY BALANCE

General steady-state process

• Q : heat transferred across the system boundary

• W : work done by the system
• zg : Potential energy
• ½u2 : kinetic energy
 THE ENERGY BALANCE
General steady-state process

• Enthalpy H = U + PV, Enthalpy can be calculated from specific and

latent heat data
• kinetic and potential energy terms are neglected which simplifies to

• This equation is usually sufficient for estimating the heating and cooling
requirements of the various unit operations involved in chemical
processes
 THE ENERGY BALANCE
General steady-state process

• For many processes the work term will be zero, or negligibly small,
and equation reduces to the simple heat balance equation

Where heat is generated in the system; for example, in a

chemical reactor
Qs = heat generated in the system, Qp = process heat added to the system
 THE ENERGY BALANCE
General steady-state process

• Thus

Qs = heat generated in the system,

Qp = process heat added to the system
H1 = enthalpy of the inlet stream,
H2 = enthalpy of the outlet stream
 Example
TOP
2

RCW
REFLUX
CW QCW
3

Feed (1000kg/h, 35˚C) FEED

water = 90% 4
acetone = 10%
1
DIST
Distillate (25˚C)
5 Acetone = 99 %
Reflux Ratio (R/D) = 10 Water = 1%
Steam (2.8 bar)
QS
condensate BTM
Bottom (100˚C)
6 Acetone < 100 ppm
 Determine the flowrate
TOP Since only trace acetone
2
at BTM, assume all
acetone goes to Dist
REFLUX
Dist(acet) = 100 kg/h
3 Dist = 100/0.99 = 101 kg/h
FEED
Feed (1000kg/h, 35˚C) Reflux = 101 x 10 = 1010 kg/h
water = 90% 4
acetone = 10%
1
DIST
Distillate (25˚C)
5 Acetone = 99 %
Water = 1%
Reflux Ratio (R/D) = 10

BTM
Bottom (100˚C)
6 Acetone < 100 ppm

Btm = 1000-101 = 899 kg/h

 2

Feed (1000kg/h, 35˚C)

water = 90% CW
acetone = 10% 3
Distillate (25˚C)
Acetone = 99 %
4 Water = 1%
1

LS
condensate Bottom (100˚C)
Acetone < 100 ppm
6

Stream 1 2 3 4 5 6
Flow Name Feed OH HEx out Reflux Dist Bottom
Water 900 10 1 899
Acetone 100 1000 100 0
Total 1000 1010 101 899
Determine the flowrate & comp.
Top = 1010 + 101 = 1111 kg/h
w = 1100 kg/h 2
a = 11 kg/h Dist = 101 kg/h
a = 100 kg/h
w = 1 kg/h

Reflux = 1010 kg/h

3
a = 1000kg/h
w = 10 kg/h
Feed (1000kg/h, 35˚C)
water (w) = 90% 4
acetone (s) = 10%
1
Distillate (25˚C)
5 Acetone = 99 %
Reflux Ratio (R/D) = 10 Water = 1%

Bottom (100˚C)
6 Acetone < 100 ppm

Btm = 1000-101 = 899 kg/h

 2

Feed (1000kg/h, 35˚C)

water = 90% CW
acetone = 10% 3
Distillate (25˚C)
Acetone = 99 %
4 Water = 1%
1

LS
condensate Bottom (100˚C)
Acetone < 100 ppm
6

Stream 1 2 3 4 5 6
Descrp Feed OH Vap HE out Refl Dist Btm
Kg/h Wt% Kg/h Wt% Kg/h Wt% Kg/h Wt% Kg/h Wt% Kg/h Wt%

Water 900 90 11 1 11 1 10 1 1 1 899 100

Acetone 100 10 1100 99 1100 99 1000 99 100 99 0 0

Total 1000 1111 1111 1010 101 899

 Heat balance
2
IN = HF + QS
OUT = QCW + HD + HB CW (23˚C)
RCW (43˚C)
HF + QS = QCW + HD + HB QCW
3

4
HF 1

5 HD
Reflux Ratio (R/D) = 10
Steam (2.8 bar)
QS
condensate

6 HB
 Heat Balance
HF + QS = QCW + HD + HB

RCW
CW QCW
Feed sensible heat (HF)= mCpΔT

Dist sensible heat (HB)

HF

HD
Reflux Ratio (R/D) = 10
Steam
QS
condensate

Reboiler Heating (QS) HB Btm sensible heat (HB)= mCpΔT

Specific Heat capacity Cp
Specific Heat capacity (ref)
Acetone = 2.15 kJ/kg.K
Water = 4.19 kJ/kg.K
Heat capacities of Feed, Dist, Btm streams

CpFeed
= 2.15(0.10) + 4.19(0.90)
= 3.98 kJ/kg.K 3
CpDist
Feed (1000kg/h, 35˚C) = 2.15(0.99) + 4.19(0.01)
water (w) = 90% 4 = 2.17 kJ/kg.K
acetone (s) = 10%
1
Distillate (25˚C)
5 Acetone = 99 %
Reflux Ratio (R/D) = 10 Water = 1%
Steam
QS
condensate
Bottom (100˚C) CpBtm
6 Acetone < 100 ppm
= 2.15(0.01) + 4.19(0.99)
= 4.17 kJ/kg.K
 Determine Heat flow
HF + QS = QCW + HD + HB

CW RCW
Feed sensible heat (HF)= mCpΔT
HF = (1000kg/h)(3.98kJ/kg˚C)(35-25)˚C
HF = 39,800 kJ/h
QCW = ? kJ/h

Dist sensible heat (HB)

HD = (101)(2.17)(25–25)˚C
HF HD = 0 kJ/h

HD
Reflux Ratio (R/D) = 10
Steam
QS
condensate

HB Btm sensible heat (HB)= mCpΔT

HF = (899kg/h)(4.17kJ/kg˚C)(100–25)˚C
HF = 281,162 kJ/h
Stream 1 2 3 4 5 6
Descrp Feed OH HEx Ref Dist Btm
Kg/h Wt% Kg/h Wt% Kg/h Wt% Kg/h Wt% Kg/h Wt% Kg/h Wt%

Water 900 90 11 1 11 1 10 1 1 1 899 100

Acetone 100 10 1100 99 1100 99 1000 99 100 99 0 0

Total 1000 1111 1111 1010 101 899

Stream 1 2 3 4 5 6
Temp 40 56.5 25 25 25 100
Pressure

Cp 3.98 2.17 2.17 2.17 4.17

[kJ/K.kg]
Latent - 639 - - - -
[kJ/kg]
Sensible 39.8 68.4 - - - 313
[kJ/kg]
Enthalpy 39,800 785,649 0 0 0 281,162
[kJ/h]

Heat Exchanger duty = ? kJ/h Reboiler duty = ? kJ/h

 Determine condenser duty QCW
Vapor flowrate at TOP Vapor temp at TOP?
= Reflux + Dist TOP boiling point of acetone
2
= 1010 kg/h +101 kg/h
= 1111 kg/h
QCW

Feed (1000kg/h, 35˚C)

water (w) = 90% 4
acetone (s) = 10%
1
Distillate (25˚C)
5 Acetone = 99 %
Reflux Ratio (R/D) = 10 Water = 1%
Steam
QS
condensate
Bottom (100˚C)
6 Acetone < 100 ppm
Boiling point of acetone/water
VLE Diagram
 Determine condenser cooling QCW
Heat balance at condenser IN
HTOP = HRefl + HDist + Qcw 56.5˚C, vapor 1111kg/h, 56.5˚C
2
RCW
QCW
QCW CW

OUT
1111kg/h, 25˚C
3
25°C, liquid
Feed (1000kg/h, 35˚C)
water (w) = 90% 4
acetone (s) = 10% 1
Distillate (25˚C)
5 Acetone = 99 %
Reflux Ratio (R/D) = 10 Water = 1%
Steam
QS
condensate
Bottom (100˚C)
6 Acetone < 100 ppm
Calculate the specific enthalpy of the TOP vapor at 56.5˚C
(330K, 1111 kg/h) – assuming complete condensation

HTOP Latent Heat

= m(Hv)
= m(0.01·Hvw + 0.99·Hva)
= 1111kg/h·(0.01x2500 + 0.99x620) kJ/kg
= 709,707 kJ/h
HTOP Sensible Heat (from 56.5˚C  25˚C)
= mCpΔT
= 1111kg/h (2.17kJ/kg˚C)(56.5–25˚C)
= 75,942 kJ/h
HTOP Latent Heat + Sensible Heat
= 709,707 + 75,942
= 785,649 kJ/h
 Determine condenser cooling QCW
HTOP = 785649 kJ/h
2
Heat balance at condenser
HTOP = HRefl + HDist + Qcw
HTOP = 0 + 0 + Qcw QCW = 785,649 kJ/h
Qcw = 785649 kJ/h
3

Feed (1000kg/h, 35˚C)

water (w) = 90% 4
acetone (s) = 10% 1
Distillate (25˚C)
5 Acetone = 99 %
Water = 1%
Steam
QS
condensate
Bottom (100˚C)
6 Acetone < 100 ppm
 Determine reboiler heating QS
HTOP = 785649 kJ/h
HF + QS = QCW + HD + HB 2

QCW = 785649 kJ/h

Feed (1000kg/h, 35˚C)

water (w) = 90% 4
acetone (s) = 10% 1
Distillate (25˚C)
5 Acetone = 99 %
Water = 1%
Steam
QS
condensate
Bottom (100˚C)
6 Acetone < 100 ppm
 Determine reboiler heating QS
HF + QS = QCW + HD + HB

CW RCW
Feed sensible heat (HF)= mCpΔT
HF = (1000kg/h)(3.98kJ/kg˚C)(35-25)˚C
HF = 39,800 kJ/h
QCW = 785,649 kJ/h

Dist sensible heat (HB)

HD = (101)(2.17)(25–25)˚C
HF HD = 0 kJ/h

HD
Reflux Ratio (R/D) = 10
Steam
QS
condensate

Reboiler Heating (QS) HB Btm sensible heat (HB)= mCpΔT

QS = 785649 + 0 + 281162 – 39800 HF = (899kg/h)(4.17kJ/kg˚C)(100–25)˚C
QS = 1,027,011 kJ/h HF = 281,162 kJ/h
Stream 1 2 3 4 5 6
Descrp Feed OH HEx Ref Dist Btm
Kg/h Wt% Kg/h Wt% Kg/h Wt% Kg/h Wt% Kg/h Wt% Kg/h Wt%

Water 900 90 11 1 11 1 10 1 1 1 899 100

Acetone 100 10 1100 99 1100 99 1000 99 100 99 0 0

Total 1000 1111 1111 1010 101 899

Stream 1 2 3 4 5 6
Temp 40 56.5 25 25 25 100
Pressure

Cp 3.98 2.17 2.17 2.17 4.17

[kJ/K.kg]
Latent - 639 - - - -
[kJ/kg]
Sensible 39.8 68.4 - - - 313
[kJ/kg]
Enthalpy 39,800 785,649 0 0 0 281,162
[kJ/h]

Heat Exchanger duty = 790,000 kJ/h Reboiler duty = 1,030,000 kJ/h

Q. How much steam and CW
1. STEAM (assuming steam totally condense)
Supply of saturated steam pressure = 2.8 bar
From steam table, specific enthalpy of evaporation of steam
(HV) = 2170 kJ/kg, then what is the required supply of steam
(in kg/h)

supply steam flowrate

2. CW
Temperature difference between CW and RCW, ΔT = 43 – 23 = 20˚C
Q. How much steam and CW
1. STEAM (assuming steam totally condense)
Supply of saturated steam pressure = 2.8 bar
From steam table, specific enthalpy of evaporation of steam
(HV) = 2170 kJ/kg, then what is the required supply of steam
(in kg/h)

supply steam flowrate

QS / Hv = 1,027,011 kJ/h = 473 kg/h
2170 kJ/kg
2. CW
Temperature difference between CW and RCW, ΔT = 43 – 23 = 20˚C

then, the amount of CW supplied to heat exchanger

CW flowrate = QCW / (Cp x ΔT)
= _____785649 kJ/h____= 9386 kg/h
(4.185 kJ/kg˚C x 20˚C)
Specific Heat Capacity Cp calculation

For solids and gases, specific heat capacity of the material (Cp)
is usually expressed as an empirical power series equation
 Cp calculation (Perry’s Handbook)
A) Perrys (Table 2-196 : Heat capacities of inorganic and organic liquids)
mw T,K C1 C2 C3 C4 C5 J/kmol.K kJ/kmol.K kJ/kg.K
Water 18 298 2.76E+05 -2.09E+03 8.125 -1.41E-02 9.37E-06 7.58E+04 75.84 4.213
acetone 58 298 1.36E+05 -1.77E+02 2.83E-01 6.89E-04 0.00E+00 1.26E+05 126.22 2.176
methanol 32 298 1.06E+05 -3.62E+02 9.38E-01 0 0 8.12E+04 81.15 2.536
ethanol 46 298 1.03E+05 -1.40E+02 -3.03E-02 2.04E-03 0 1.12E+05 112.24 2.440
formaldehyde 30 298 6.19E+04 2.83E+01 0.00E+00 0.00E+00 0 7.03E+04 70.33 2.344

B) Perrys (Table 2-198 : Heat capacities of inorganic and organic compounds in ideal gas state)

mw T,K C1 C2 C3 C4 C5 J/kmol.K kJ/kmol.K kJ/kg.K

Water 18 373 3.34E+04 2.68E+04 2.61E+03 8.90E+03 1.17E+03 3.40E+04 34.02 1.890
acetone 58 343 5.70E+04 1.63E+05 1.61E+03 9.68E+04 7.32E+02 8.23E+04 82.32 1.419
methanol 32 373 3.93E+04 8.79E+04 1.92E+03 5.37E+04 896.7 4.95E+04 49.53 1.548
ethanol 46 373 4.92E+04 1.46E+05 1.66E+03 9.39E+04 744.7 7.74E+04 77.38 1.682
formaldehyde 30 373 3.33E+04 4.95E+04 1.87E+03 2.81E+04 934.9 3.81E+04 38.13 1.271
 Cp calculation (Perry’s Handbook)
A) Perrys (Table 2-196 : Heat capacities of inorganic and organic liquids)
mw T,K C1 C2 C3 C4 C5 J/kmol.K kJ/kmol.K kJ/kg.K kcal/kg.K
Water 18 298 2.76E+05 -2.09E+03 8.125 -1.41E-02 9.37E-06 7.58E+04 75.84 4.213 1.01
acetone 58 298 1.36E+05 -1.77E+02 2.83E-01 6.89E-04 0.00E+00 1.26E+05 126.22 2.176 0.52
methanol 32 298 1.06E+05 -3.62E+02 9.38E-01 0 0 8.12E+04 81.15 2.536
ethanol 46 298 1.03E+05 -1.40E+02 -3.03E-02 2.04E-03 0 1.12E+05 112.24 2.440
HCHO 30 298 6.19E+04 2.83E+01 0.00E+00 0.00E+00 0 7.03E+04 70.33 2.344

B) Perrys (Table 2-198 : Heat capacities of inorganic and organic compounds in ideal gas state)

mw T,K C1 C2 C3 C4 C5 J/kmol.K kJ/kmol.K kJ/kg.K

Water 18 373 3.34E+04 2.68E+04 2.61E+03 8.90E+03 1.17E+03 3.40E+04 34.02 1.890
acetone 58 343 5.70E+04 1.63E+05 1.61E+03 9.68E+04 7.32E+02 8.23E+04 82.32 1.419
methanol 32 373 3.93E+04 8.79E+04 1.92E+03 5.37E+04 896.7 4.95E+04 49.53 1.548
ethanol 46 373 4.92E+04 1.46E+05 1.66E+03 9.39E+04 744.7 7.74E+04 77.38 1.682
HCHO 30 373 3.33E+04 4.95E+04 1.87E+03 2.81E+04 934.9 3.81E+04 38.13 1.271
 Cp calculation from “Elementary
Principles of Chemical Properties”
B) Elementary Principles of Chemical Process (Table B.2)
MW T, degC a b c d kJ/mol.C J/mol.C J/g.C

water (l) 18 30 7.54E-02 0.0754 75.40 4.189

water (g) 18 100 3.35E-02 6.88E-06 7.60E-09 -3.59E-12 0.0342 34.22 1.901

acetone (l) 58 30 1.23E-01 1.86E-04 0.1286 128.58 2.217

Exercise: Calculate
methanol (l) 32 30 7.59E-02 1.68E-04 0.0809 80.91 2.528
the specific heat
methanol (g) 32 66 4.29E-02 8.30E-05 -1.87E-08 -8.03E-12 0.0483
capacity48.32
(J/g.C) 1.510
of
ethanol (l) 0 degC 46 0 1.03E-01 30˚C water
0.1031 103.10(l) 2.241
and
ethanol (l) 100 degC 46 100 1.59E-01 100˚C158.80
0.1588 water(g) 3.452

ethanol (g) ~1200C 46 75 6.13E-02 1.57E-04 -8.75E-08 1.98E-11 0.0726 72.65 1.579

formaldehyde (g) 30 30 3.43E-02 4.27E-05 0.00E+00 -8.69E-12 0.0356 35.56 1.185

 Mean Heat Capacities (Cpm)
EXERCISE :
What is the heat extracted from the gas in cooling from 300 to 130 C

vol%
O2 6.3 190oC

CO 1.3 methanol
N2 76.6 Gas
300oC
vol%
MeOH 0.1
O2 6.3 HCHO 7.8 Gas
CO 1.3
vaporizer 130oC
N2 76.6 H2O 7.9
MeOH 0.1
TOTAL 100 blower
HCHO 7.8
H2O 7.9 80oC
TOTAL 100
 T,˚C MW a b c d kJ/mol.C kJ/kg.C
Water (l) 25 18.016 7.54E-02 0.0754 4.189
Water (g) 300 18.016 3.35E-02 6.88E-06 7.60E-09 -3.59E-12 0.0361 2.006
CO (g) 300 28.01 2.90E-02 4.11E-06 3.55E-09 -2.22E-12 0.0304
CO2 (g) 300 44.01 3.61E-02 4.23E-05 -2.89E-08 7.46E-12 0.0464
MeOH (l) 30 32.04 7.59E-02 1.68E-04 0.0809 2.528
MeOH (g) 300 32.04 4.29E-02 8.30E-05 -1.87E-08 -8.03E-12 0.0659 2.059
O2 (g) 300 32 2.91E-02 1.16E-05 -6.08E-09 1.31E-12 0.0321
N2 (g) 300 28.02 2.90E-02 2.20E-06 5.72E-09 -2.87E-12 0.0301
air (g) 300 29 2.89E-02 4.15E-06 3.19E-09 -1.97E-12 0.0304
HCHO 300 30.03 3.43E-02 4.27E-05 0.00E+00 -8.69E-12 0.0468

T (degC) 130 300

J/molC J/molC Calculate Cp
O2 (g)
CO (g)
Heat capacity by temperature chg
N2 (g)
MeOH (g)
HCHO
Water (g)
 T,˚C MW a b c d kJ/mol.C
Water (l) 25 18.016 7.54E-02 0.0754
Water (g) 300 18.016 3.35E-02 6.88E-06 7.60E-09 -3.59E-12 0.0361
CO (g) 300 28.01 2.90E-02 4.11E-06 3.55E-09 -2.22E-12 0.0304
CO2 (g) 300 44.01 3.61E-02 4.23E-05 -2.89E-08 7.46E-12 0.0464
MeOH (l) 30 32.04 7.59E-02 1.68E-04 0.0809
MeOH (g) 300 32.04 4.29E-02 8.30E-05 -1.87E-08 -8.03E-12 0.0659
O2 (g) 300 32 2.91E-02 1.16E-05 -6.08E-09 1.31E-12 0.0321
N2 (g) 300 28.02 2.90E-02 2.20E-06 5.72E-09 -2.87E-12 0.0301
air (g) 300 29 2.89E-02 4.15E-06 3.19E-09 -1.97E-12 0.0304
HCHO 300 30.03 3.43E-02 4.27E-05 0.00E+00 -8.69E-12 0.0468

T (˚C) 130 300

J/molC J/molC Calculate Cp
O2 (g) 30.51 32.06
CO (g) 29.54 30.44
Heat capacity by temperature chg
N2 (g) 29.38 30.10
MeOH (g) 53.39 65.93
HCHO 39.81 46.85
Water (g) 34.47 36.11
Mean Heat Capacities (multi components)
Heat extracted for each component =
= Mc (Cpm,300C x 300) – Mc(Cpm,130C x 130) Methanol (g)
= Mc (Cpm,300C x 300 – Cpm,130C x 130)

Cp of each component Waste gas 190oC

T (˚C) 130 300 Vol%
Methanol(l)
J/molC J/molC
O2 6.3 300oC
O2 (g) 30.51 32.06
CO 1.3

CO (g) 29.54 30.44

N2 76.3 130oC
N2 (g) 29.38 30.10
MeOH 0.1 vaporizer
MeOH (g) 53.39 65.93
HCHO 7.8

HCHO 39.81 46.85

H2O 7.9
TOTAL 100 80oC
Water (g) 34.47 36.11

blower

Ambient air
 Mean Heat Capacities (Cpm)
Heat extracted for each component =
= Mc (Cpm,300 x 300 – Cpm,130 x 130)
O2 6.3 (32.06 x 300 – 30.51 x 130) = 35227
CO 1.3 (30.44 x 300 – 29.54 x 130) = 6658
N2 76.6 (30.10 x 300 – 29.38 x 130) = 399132
MeOH 0.1 (65.93 x 300 – 53.39 x 130) = 1558
HCHO 7.8 (46.85 x 300 – 39.81 x 130) = 69448
H2O 7.9 (36.11 x 300 – 34.47 x 130) = 50302
Calculated Cp 562,325 J/ 100mol
562 kJ/100mol
Cp of each component Waste gas 5.6 kJ/mol
T (˚C) 130 300 Vol%
… is the heat extracted
J/molC J/molC O2 6.3
from the gas in cooling
O2 (g) 30.51 32.06 CO 1.3
CO (g) 29.54 30.44 from 300 to 130 C
N2 79.3
N2 (g) 29.38 30.10 MeOH 0.1
MeOH (g) 53.39 65.93
HCHO 7.8
HCHO 39.81 46.85
H2O 7.9
Water (g) 34.47 36.11
TOTAL 100