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Energy Balance

Winarsih
Minta Yuwana
Pantjawarni P.
Tantular N.

10/9/98 1
Konsep
Sistem, Lingkungan, Batas sistem
Property
Extensive property (variabel, parameter)
Intensive property (variabel, parameter)
Energy
Energy yang selalu melekat dengan massa
Energy yang dapat berpindah tanpa massa
Persamaan balance energy

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System, Surrounding, Boundary
Heat or power

Input Output
flow flow
streams
system streams

boundary
surrounding
Internal details of a system is disregarded
Only passage of material and energy across
boundary is concerned.

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System classification:
Open system
mass and energy can penetrate across the system
boundary
Closed system
mass can not move across the system boundary
energy can penetrate across the system boundary
Isolated system
mass and energy can not penetrate the system
boundary
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Types of Energy
Work (W):
meaning in everyday life:
I am going to work
a form of transfer of energy
work cannot be stored
transferred without accompanied by mass
work is path function
for mechanical force: W = F.dS

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Example:
An ideal gas is contained in a cylinder with
a frictionless piston plug. Initially its
volume is 0.2 m3 and its pressure is 125
kPa. The gas is expanded to a volume of 0.4
m3 in two ways, (a) by heating at constant
pressure of 125 kPa, and (b) by reducing the
pressure at constant temperature of 303 K.
Calculate the works of both methods.

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Solution:
slightly manipulating the relation of W
State 2
State 2 F
W Ads pdV
State1 A State1

1. Expansion by heating at constant pressure


N J
V2 125 10 Pa 1 2 0.2m 1
3 3

m m
V

W p dV p(V2 V1 )
1Pa 1N
25kJ
1

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2. Expansion at constant temperature
V2 V2 nRT V2
W pdV dV nRT ln
V1 V1 V V1
V2
p1V1 ln
V1
N 3 0.4 J
125kPa 1 2
0 .2m ln 1
m 0.2 m
17.33kJ
1Pa 1N

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Types of Energy
Heat (Q):
often confused with temperature
a form of transfer of energy due to the difference
of temperature
can not be stored
transferred without accompanied by mass transfer
rate of transfer correlates linearly to temperature
difference:
Q = UA(Tsystem- Tsurrounding)
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Types of Energy
Kinetic Energy (K):
associated with mass movement/speed
K = 1/2 mv2
can be stored
can not be transferred without mass

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Example:
Benzene ( = 0.879 kg/L) flows through an
orifice that is 0.8 cm in diameter at the rate
of 4.63 m3/hr. What is the kinetic energy of
the fluid in J/kg?
Solution:
3
m 1 hr
4.63
hr 3600 s
Velocity through orifice = 2
5.526 m/s.
0.008
m2
Kinetic energy for 1 kg = 4

m 2
1N 1J
2 1 kg 5.526 15.27 J
1 2

s2 kg.m 1 N.m
1
s2
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Types of Energy

Potential Energy (P):


associated with gravitational field (altitude),
magnetic field, spring force, etc.
P = mgh
can be stored
can not be transferred without mass

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Example:
Water is pumped to the third floor from the
reservoir at the ground. The total elevation
is 15 m. What is the specific potential
energy of the water at the third floor with
respect to the reservoir level?

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15 m

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Solution:
the water level in the reservoir as the
reference plane
h = 15 m.
The specific potential energy is
9.807 m 15 m 1 kg 1 N 1J
P 2 2
147.1 J/kg
s 1 kg 1 kg.m/s 1 N.m

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Types of Energy

Internal energy (U):


associated with temperature and molecular
arrangement
can not be measured directly
absolute quantity is (still) unknown, only
relative quantity is used
can be stored
can not be transferred without mass

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Calculation of Internal Energy per
Unit Mass ()
Calculated from measurable variables:
temperature, pressure, compositions, etc.
Use exact differential property of point or
state property
Follow the phase rule
F = C -P +2
for a pure component, F = 2, for example T and
V
10/9/98 17
Calculation of Internal Energy per Unit Mass ()

U U (T , V )

U




U


dU dT dV


T V V T



By definition


U

Cv


T





V

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Calculation of Internal Energy per Unit Mass ()

For most practical purposes:


U
dV 0
V T
Changes in the internal energy ()
T2

U U 2 U1 T Cv dT
1

Only the difference can be calculated,


not the absolute value !!

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Enthalpy (H)
see p.372
Combination of two variables U and pV.
Defined as
H U pV

The term enthalpy replace obsolete terms


heat content or total heat
Enthalpy is state or point state property.
Exact differential property apply.

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Enthalpy (H)

Suppose enthalpy for a unit mass ( H )


H H (T , p )
H H
dH dT dp
T p p T
By definition
H
Cp
T p

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Enthalpy (H)

For most practical purposes at modest


pressure or at constant pressure
H
dp 0
p T
Changes in enthalpy:
T2

H H 2 H1 T C p dT
1

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Enthalpy (H)

Enthalpy has no absolute value; only


changes (relative) in enthalpy can be
calculated.
A reference set of conditions are required to
calculate the value of enthalpy
the value of enthalpy at reference conditions is
defined as zero, but actually it is not.
Any given value of enthalpy is relative
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Enthalpy (H)

The reference values cancel out in


calculation of enthalpy changes, as long as
the reference conditions used are the same
H2
H
H1

Reference value = 0

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Enthalpy (H)

Incorrect use of different Correct use of different


reference conditions reference conditions
H2 H2

H1 H H1 H

Htotal=H +Href

Ref.1 Href
Ref.1
Ref.2 Ref.2
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Point (or state) functions
Examples: U, H, T, p,
Their values depend only on
the state (T, p, phase, and 2
composition) of the material
Their values do not depend 1
on how the material reached
the particular state

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Example:
One kilogram mole of steam at 150C and
150 kPa is expanded to 210C and 100 kPa.
Thereafter it is condensed to water at 25C
and 100 kPa. What is the overall (a)
enthalpy change and (b) internal energy
change per kilogram mole of steam for the
process?

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Solution:
The overall process

p kPa
1
150

100 2
3

25 150 210 T

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Internal energy and enthalpy are state functions,
the overall changes can be calculated from the initial
state and the final state
Initial state: state 1
Vapor: at 150C and 150 kPa
H1 = 2772.9 kJ/kg
V1 = 1.2856 m3/kg
H1 = U1 + p1V1 2772.9 = U1 + 1501.2856
U1 = 2772.9 192.8 = 2580.1 kJ/kg

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Final state: state 2
Liquid at 25C and 100 kPa
H2 = 104.9 kJ/kg v2 = 0.001 m3/kg
U2 = 104.9 - 1000.001 = 104.8 kJ/kg

The overall difference


H = 104.9 2772.9 = -2668.0 kJ/kg
U = 104.8 2580.1 = -2475.3 kJ/kg
10/9/98 30
Presentation of enthalpy data
Most of the enthalpy data available are
from experimental works
Various ways of presenting enthalpy data
Table: Steam Table
Complicated graphics or chart: Psychrometric
Chart
Empirical formula

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The values of enthalpy data are only
relative values toward a set of reference
states.
The value of enthalpy at reference states is
defined to have a value of zero.
Unfortunately, different source of data could
use different reference state.

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Calculation of the enthalpy changes

The enthalpy changes from state 1 to state 2


is obtained by subtracting the enthalpy at
state 2 with the enthalpy at state 1.

H 2
H ref H 1 H ref H 2 H 1

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The phase of the substance at state 2 can be
different from state 1,
the substance undergoing phase transitions during
its changes from state 1 to state 2.
The values of enthalpy change at phase transition
occur during melting, crystal structure change,
boiling, and sublimation.
For pure substances the phase transition occur at
single temperature, but for mixtures it is a range.

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The values of the enthalpy data should be
examined whether they already contain the
values of enthalpy changes at phase
transitions.
Commonly in a graphical presentation as a chart
the values already include the values of transitional
phase.
For others it usually should be calculated
separately.
10/9/98 35
Single phase

Phase change

Temperature

10/9/98 36
Recently, many enthalpy data are predicted
analytically using much better
thermodynamics theory.
Their accuracy increase so much that they can
beat or comparable to the accuracy of
experimental works.

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Example:
Saturated enthalpy, kJ/kg
T,C
liquid vapor

The steam 50 209.34 2591.32

70 293.02 2626.11
tables 80 334.95 2643.02

90 376.97 2659.54

100 419.10 2675.59

110 461.36 2691.09

120 503.78 2705.96

130 546.39 2720.11

140 589.20 2733.47

150 632.25 2745.95

160 675.57 2757.47

170 719.21 2767.94

180 763.19 2777.27

190 807.57 2785.37

200 852.39 2792.13

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What is the value of enthalpy difference between
saturated water at 50C and saturated steam at 200C?
Solution:
State 1: saturated water T1 = 50C
H1 = 209.34 kJ/kg
State 2: saturated vapor T2 = 200C
H2 = 2792.13 kJ/kg
H = 2792.13 209.34 = 2582.80

10/9/98 39
Calculation of enthalpy changes without
phase transitions

Can be calculated from the simplified heat


capacity relationship
T2

H 2 H 1 H C p dT
T1

Commonly called: sensible enthalpy changes


For most substances Cp is not constant but
function of temperature.

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4.2 Heat capacity ()
Useful for calculation of enthalpy
Two have been defined
U




H
Cp

Cv

T





V p

Heat capacity is not constant with


temperature, but vary
Unit: J/(kg-mol.K) Btu/(lb-mol.oF)
J/(kg.K) Btu/(lb.oF)
10/9/98 41
Heat capacity

Heat capacities do
Phase transitions
not hold on phase
Cp liquid
transitions
Solid
II gas
Heat capacities are
Solid continuous function
I
0 only in the region
0 T(K)
between phase
transitions
10/9/98 42
Heat capacity

Heat capacities of ideal gases


see Table 4.1 p.379
Heat capacities of real gases
for example: combustion gases, see Fig.4.7
p.379
Heat capacity per mole of ideal gas mixture
n
C pavg xiC pi
i 1

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Heat capacity
Non ideal gas, liquids, mixtures, solutions:
Refer to experimental data presented as tables,
charts, or equations
Use estimation technique listed in the literature

10/9/98 44
Heat capacity Model
Most of the heat capacities equations are
empirical models
Common forms are
C p a bT cT 2 dT 3 (1)

C p a bT cT 2 (2)

10/9/98 45
Heat capacity :
Calculation of Cp from enthalpy data
See example 4.7 p.382
Equation of enthalpy given by Kelley, U.S.
Bureau for titanium tetrachloride
H H 298 25.4T 0.12 103T 2 2.36 105 T 1 8390

Equation for Cp
dH
Cp 25.45 0.24 103T 2.36 105 T 2
dT

10/9/98 46
Heat capacity :
Calculation of Cp from enthalpy data
See example 4.8
Experimental data
Fitting equation of
heat capacity to Cp
experimental data C p
of
Use of non linear u a ti on
eq
regression to ss ed
re
estimate the Re
g

parameters of the
T
equation
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4.2-1 Estimation of Heat Capacity
See p.383
Solids
only very rough available
Kopps rule (1864) should only be used when
nothing is available (see Table 4.2)
example: Cp Na2SO4.10H2O =
2(6.2) + 1(5.4) + 14(4.0) + 20(2.3) = 119.8 cal/(g
mol)(oC)
Consult Reid or Perrys Handbook for others
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4.2-1 Estimation of Heat Capacity

Liquids
Aqueous solutions:
use experimental data
very rough estimate: use Cp of water fraction alone.
Example: Cp of 21.6% of NaCl
(1- 0.216) Cp H2O = 0.784 cal/(g)(oC)
experimental data at 25 oC = 0.806 cal/(g)(oC)
Hydrocarbons: see Appendix K
Organic liquids: .
10/9/98 49
4.2-1 Estimation of Heat Capacity

Liquids
Organic liquids: a simple and reasonably
accurate
Cp = kMa
Pachaiyappen et al. Give a set of (k,a), see
p.384

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4.2-1 Estimation of Heat Capacity

Gases and vapor


Petroleum vapor:
(4.0 s )(T 670)
Cp
6450
Kothari-Doraiswamy equation: for
interpolation between two temperature
Cp = a + b log10 Tr
See Reid et al. for additional data

10/9/98 51
Estimation of Heat Capacity

Pure Organic Liquids and Vapours


Available as Addins program for
Excell. See ChE Tools on Excell
Menu Taskbar
4.3 Calculation of enthalpy changes
without change of phase
See p.386
H 2 T2
H H 1
d
H C dT
T1 p
for
2
C p a bT cT
T2

H T a bT cT 2 dT

1

b 2
2
2 c 3

a (T2 T1 ) T2 T1 T2 T13
3

10/9/98 53
4.3 Calculation of enthalpy changes
without change of phase

Cp

T1 T T2

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4.3.2 Tabular data

See Table 4.3, 4.4, 4.5 and Appendix D

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4.3-3 Graphical Presentation of Enthalpy Data

Chart are drawn with various coordinates


p versus H
p versus V
p versus T
H versus S
See Table 4.6 and Perrys Handbook

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4.4 Enthalpy Changes for Phase
Transitions
4.4-2 Heat of Vaporization
Clausius-Clapeyron equation
Reduced form of the Clapeyron equation
Chens equation
4.4-3 Reference Substance Plots
Duhring plot
Othmer plot

10/9/98 57
Enthalpy Data
Pure Organic Liquids and Vapours
Available as Addins program for
Excell. See ChE Tools on Excell
Menu Taskbar
Example:
The hot flue gas has the following composition (mole
%)
CO2 10.5%
CO 1.5%
O2 5.6%
N2 82.4%
Total 100.0%
The gas is flowing through an economizer where the
gas is cooled from the temperature of 500C to the
temperature of 250C.
How much Joules the gas loss its enthalpy energy per
100 moles? What its loss per kg?
10/9/98 59
Solution
Heat capacity equations for the gas
component are (in J/ (moles C)
N2: C p 29.00 0.2199 10 2 T 0.5723 10 5 T 2 2.871 10 9 T 3
O2: C p 29.10 1.158 10 2 T 0.6076 10 5 T 2 1.311 10 9 T 3
CO: C p 28.95 0.4110 10 2 T 0.3548 10 5 T 2 2.220 10 9 T 3
CO2: C p 36.11 4.233 10 2 T 2.887 10 5 T 2 7.464 10 9 T 3

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Taking the integral from 500 to 250 for each
component
250
H N 2 (29.00 0.2199 10
2
T 0.5723 10 5 T 2 2.871 10 9 T 3 )dT 7622.75J/mole
500

250
H O2 (29.10 1.158 10
2
T 0.6076 10 5 T 2 1.311 10 9 T 3 ) dT 8158.31J/mole
500

250
H CO (28.95 0.4110 10
2
T 0.3548 10 5 T 2 2.220 10 9 T 3 )dT 7719.65J/mole
500

250
H CO2 (36.11 4.233 10
2
T 2.887 10 5 T 2 7.464 10 9 T 3 )dT 12052.7J/mole
500

10/9/98 61
Arrange the calculation in spreadsheet format:
mole
Component MW H, J/mole moles H, J mass
fraction
N2 28 -7622.75 0.824 82.4 -628115 2307.2
O2 32 -8158.31 0.056 5.6 -45686 179.2
CO 28 -7719.65 0.015 1.5 -11579 42.0
CO2 44 -12052.7 0.105 10.5 -126554 462.0
Total 1.000 100.0 -811934 2990.4

Losses/unit -8119.3
-271.5
J/mole J/gr

Total energy loss due to enthalpy changes is 811934 J or


811.934 kJ and the lost per kg is = 2990.4
10/9/98 62
Calculation of enthalpy changes
accompanied by phase changes
The total value of the enthalpy changes is obtained by
separating the phase changes from the single phases.
Adding up each change will give the total changes.
The various enthalpy changes due to a phase transition
are termed as:
Heat of fusion Solid changes into liquid
Heat of vaporization Liquid to vapor
Heat of condensation Vapor to liquid
Heat of sublimation Solid to vapor
The old name of enthalpy changes due to a phase change
is latent heat.

10/9/98 63
Example:
What is the enthalpy change of 1 kg of water
from ice at 0C to vapor at 120C and 100
kPa?
Data:
Hf = 335 J/g at 0C and p* or at 101.3 kPa
Hv = 2256 J/g at 100C and 101.3 kPa
The heat capacity equations
Liquid [J/(gr mol)(K)]:
C p 18.296 47.212 10 2 TK 133.88 10 5 TK2 1314.2 10 9 TK3
Vapor [J/(gr mol)(C)]:
C p 33.46 0.6880 10 2 T o C 0.7604 10 5 T o2C 3.593 10 9 T o3C

10/9/98 64
T C
E
120

Cp Vap
apply or

Cp C D
100
apply at
Liqu 100C
id
A B F
0
Soli at at
d 0C 0C

10/9/98 65
Solution:
To reach the final state 2 (corresponding to
point E) there are two routes,
ABCDE
ABFDE
enthalpy is a state function, the choice of the routes
will not change the value of the final enthalpy.
Suppose the route ABCDE is
chosen to calculate.

10/9/98 66
Path Phenomena Calculation
A to B Melting of ice Heat of fusion
B to C Heating of liquid Enthalpy changes due to
water from 0C to temperature change.
100C Use liquid Cp.
C to D Vaporization at Heat of vaporization
100C and 100
kPa
D to F Heating up the vapor Enthalpy changes due to
from 100C to temperature change.
120C at constant Use vapor Cp.
pressure
10/9/98 67
H overall H AB H BC H CD H DE

H f at 0 C H sensible 0 100 C H v at 100 C H sensible 100 C 120 C


373.15
335 181 (18.296 47.212 10 2 T 133.88 10 5 T 2 1314.2 10 9 T 3 )dT
273.15

120
2256 181 (33.46 0.6880 10 2 T 0.7604 10 5 T 2 3.593 10 9 T 3 )dT
100

335 418.6 2256 38.1 3048

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