Energy Balances and

Thermodynamics
Florabel R. Toro-Rodrguez, Esq, PE
Agenda
I. Terminology Associated with the Energy
Balances and Thermodynamics
II. Types of Energy
A. Work (W)
B. Heat (Q)
C. Kinetic Energy (KE)
D. Potential Energy (PE)
E. Internal Energy (U)
F. Enthalpy (H)
G. Entropy (S)
Agenda (cont.)
III. Energy Balances for Processes without Reaction
A. Closed, Unsteady-State Systems
B. Energy Balances for Closed, Steady-State Systems
C. Energy Balances for Open, Unsteady-State Systems
D. Energy Balances for Open, Steady-State Systems
E. Summary
IV. Calculation of Enthalpy Changes
A. Phase Transitions
B. Heat Capacity Equations
C. Tables and Charts to Retrieve Enthalpy Values
Agenda (cont.)
V. Applications of Energy Balances
A. Solving Energy Balances Problems in the Absence
of Chemical Reactions
B. Solving Energy Balances Problems with Chemical
Reactions
C. Applications of Energy Balances in Processes that
Include Reactions
VI. Volumetric Properties of Pure Fluids
A. PVT Behavior of Pure Substances
B. Single Phase Region
Agenda (cont.)
VII. Ideal Processes, Efficiency, and
Cycles
VIII. Gibbs Energy, Equilibrium Constant,
and Solution Thermodynamics
A. Gibbs Energy (G)
B. Equilibrium Constant (K)
C. Solution Thermodynamics
D. Heat Effects of Mixing Processes
I. Terminology
Refer to your notes
II. Types of Energy
Energy is the capacity to do work.
Types of Energy
A. Work (W)
Mechanical work
Electrical work
Shaft work
Flow work
Path function
B. Heat (Q)
Conduction
Convection
Radiation
Path function
II. Types of Energy (cont.)
C. Kinetic Energy (KE)
KE =
State function
D. Potential Energy (PE)
PE = mgh
State function
2
mv
2
1
II. Types of Energy (cont.)
E. Internal Energy (U)
Takes into account all of the molecular, atomic,
and subatomic energies

State function
dV
V
U
dT
T
U
dU
T V
|

\
|

+
|

\
|

=
2
1
T
T
V
dT C U
II. Types of Energy (cont.)
F. Enthalpy (H)
H = U + PV

State function
For an ideal gas
C
P
= C
V
+ R

dP
P
H
dT
T
H
dH
T P
|

\
|

+
|

\
|

=
2
1
T
T
P
dT C H
V
p
C
C
k =
II. Types of Energy (cont.)
G. Entropy (S)
Unusable energy or the measure of a
materials disorder
S = Q/T
S = C
P
ln(T
2
/T
1
) - Rln(P
2
/P
1
), for ideal gases
State function
III. Energy Balances for
Processes without Reaction
A. Closed, Unsteady-State System
Closed does not interchange mass with the
surroundings. W and Q can be interchanged.
Unsteady-state the state of the material changes
inside the system.
Refer to Figures III.A(1a) and (1b) of your notes.
Examples batch processes used to manufacture
specialized pharmaceuticals and polymer products
Low production quantities
III. Energy Balances for Processes
without Reaction (cont.)
B. Energy Balances for Closed, Steady-State
Systems
Closed does not interchange mass with the
surroundings. W and Q can be interchanged.
Steady-state - the state of the material does not
change inside the system.
All W done on a closed, steady-state system must be
transferred out as Q. However, the reverse is false.
Refer to Figures III.B(1a) and (1b) of your notes.
III. Energy Balances for Processes
without Reaction (cont.)
C. Energy Balances for Open, Unsteady-State
Systems
Open does interchange mass with the surroundings.
W and Q can also be interchanged.
Unsteady-state the state of the material changes
inside the system.
PV work work done by the surroundings to put a
mass of matter into or out of the system.
Enthalpy (H) the form of energy related to mass
includes the PV work term.
Examples filling of a fixed volume tank, batch
distillation without replacement of feed
III. Energy Balances for Processes
without Reaction (cont.)
D. Energy Balances for Open, Steady-
State Systems
Open does interchange mass with the
surroundings. W and Q can also be
interchanged.
Steady-state - the state of the material does
not change inside the system.
Examples refining and chemical industries
High-volume products
III. Energy Balances for Processes
without Reaction (cont.)
Summary - refer to your notes
IV. Calculation of Enthalpy
Changes
A. Phase Transitions
For a single phase
U = fn(T)
H = fn(T)
Sensible heat T 0
Latent heat T = 0
IV. Calculation of Enthalpy
Changes (cont.)
How is the overall H for a pure substance calculated?
Solid Liquid Vapor
T
m
T
v
Temperature, T
Enthalpy, H
A
B
C D
E
F
Figure IV.A(1) Enthalpy changes of a pure substance as a function of temperature.
IV. Calculation of Enthalpy
Changes (cont.)
Refer to your notes for relationships between
the slope of the vapor pressure (P

) curve and
the molar heat of vaporization ( ).
Clapeyron equation
Clausius-Clapeyron equation
Chens equation
Watson equation
vap
H

IV. Calculation of Enthalpy

Changes (cont.)
Example IV.A(1)
The vapor pressure of 2,2,4-trimethyl
pentane at several temperatures is
given.
Calculate the heat of vaporization (Btu/lb
mole) of this compound at 77F.
IV. Calculation of Enthalpy
Changes (cont.)
B. Heat Capacity Equations
Heat capacity amount of energy required to increase
the temperature of a substance by one degree, (J/mol-
K, Btu/lbm-R)
Generally, C
P
= C
V
for liquids and solids.
H = C
P
T. Why is C
P
frequently used?
C
P
= fn(T). Most equations are empirical.
For mixtures, the heat capacity is the mole-weighted
average of the heat capacity of the components

Pi
n
1 i
i
avg
P
C

x C

=
=
IV. Calculation of Enthalpy
Changes (cont.)
Example IV.B(1)
What is the enthalpy change for 1 kg of
water from -30C to 130C using the
following data:
T
f
= 0C, T
vaporization
= 100C,
H
fusion@0C
= 6.01 kJ/gmol, H
vaporization@100C
=
40.65 kJ/gmol,

Pice
= 23.7 J/gmol-C,

Pliquid water
= 75.4 J/gmol-C,

Pvapor water
= 33.9 J/gmol-C.
C

IV. Calculation of Enthalpy

Changes (cont.)
C. Tables and Charts to Retrieve Enthalpy
Values
Experimental data of pure compounds are organized
in tables, T and P being the independent variables.
Steam tables are the most common ones.
Steam tables practice exercise. Find H at 150C and
375 kPa.
Enthalpy differences can be calculated, H = H
f
- H
i
.
For compressed liquids, properties of saturated liquid
can be used as a good approximation.
V. Applications of Energy
Balances
A. Solving Energy Balance Problems in
the Absence of Chemical Reactions
Assumptions for energy balance problems
saturated liquid vapor pressure of the liquid
gas one atmosphere
EB: in out = accumulation - generation
V. Applications of Energy
Balances (cont.)
Example V.A(1)
An insulated heat exchanger is carrying
saturated steam at a pressure of 2.0 bar. An
oxygen stream at a pressure of 1.5 bar and
flowing at the rate of 150 kmol/h is to be
heated from 25C to 220C using the heat
exchanger. The average heat capacity of
oxygen is constant over the range at 30.07
kJ/kmol-C. Calculate the steam consumption.
V. Applications of Energy
Balances (cont.)
B. Solving Energy Balance Problems
with Chemical Reactions
Exothermic reaction products have less
energy than reactants, Q
out
.
Endothermic reaction products have more
energy than reactants, Q
in
.
V. Applications of Energy
Balances (cont.)
- standard heat of formation.
denotes standard state, 25C and 1 atm.
It is defined as one mole of a compound formed
from its constituent elements in their standard state.
The standard heat of formation is negative for
exothermic reactions.
The reaction can be a fictitious process. Remember
that H is a state function.
The heat of formation is zero in the standard state for
each stable element.
o
f
H

V. Applications of Energy
Balances (cont.)
- standard heat of reaction
denotes standard state, 25C and 1 atm.
It is defined as one mole of a compound that reacts
when stoichiometric quantities of reactants in the
standard state react completely to produce products in
the standard state.

i
species i stoichiometric coefficient ratio
o
rxn
H

o
i f,
reactants
i
i
o
i f,
products
i
i
o
rxn
H

=
V. Applications of Energy
Balances (cont.)
Thermodynamics routes
Reactants,
T
Reactants,
H =
H(25C) - H(T)
Products,
T
Reactants,
25C
Hrxn, 25C Products,
25C
Products,
H=
H(T) - H(25C)
Hrxn, T
Figure V.B(1) Steps for the calculation of the enthalpies comprising Hrxn
V. Applications of Energy
Balances (cont.)
Example V.B(1)
Public concern about the increase in the carbon dioxide in
the atmosphere has led to numerous proposals to
sequester or eliminate the carbon dioxide. An inventor
believes he has developed a new catalyst that can make
the gas phase reaction
CO
2
(g) + 4H
2
(g) 2H
2
O(g) + CH
4
(g)
proceed with 100% conversion of CO
2
. The source of the
hydrogen would be from the electrolysis of water using
electricity generated from solar cells. Assume
stoichiometric amounts of the reactants enter the reactor.
Calculate the heat of reaction if the gases enter and
leave at 1 atm and 500C.
V. Applications of Energy
Balances (cont.)
Example V.B(2)
One mol of CO
2
is entering at 800 K and
reacts with 4 mol of H
2
entering at 298 K.
Only 70% conversion of the CO
2
occurred. The products exited from the
reactor at 1000 K. Calculate the heat
transfer to or from the reactor.
V. Applications of Energy
Balances (cont.)
- standard heat of combustion
denotes standard state, 25C and 1 atm.
The compound is oxidized with oxygen or some other
substance to the products CO
2
(g), H
2
O(l), HCl(aq),
and so on.
Zero values of are assigned to certain of the oxidation
products as, for example, CO
2
(g), H
2
O(l), HCl(aq), and
to O
2
(g) itself.
Stoichiometric quantities are assumed to react
completely.
o
c
H
V. Applications of Energy
Balances (cont.)
The relation between and is
=
where n
i
is the species i number of moles.
o
rxn
H

o
c
H
(

products
i
reactants
i
o
i c, i
o
i c, i
H

n H

n
o
rxn
H
V. Applications of Energy
Balances (cont.)
Heating value the negative of the
standard heat of combustion for a fuel,
such as coal or oil.
Depending upon the state of the water in
the combustion products
LHV [lower (net) heating value] vapor
HHV [high (gross) heating value] - liquid
V. Applications of Energy
Balances (cont.)
Example V.B(3)
For CO(g) + H
2
O(g) H
2
(g) + CO
2
(g)
calculate the from the heat of
combustion data.
o
rxn
H
V. Applications of Energy
Balances (cont.)
Example V.B(4)
In a waste-to-energy facility, a
concentrated solution of urea is sprayed
into the furnace in the selective non-
catalytic reduction of nitrogen oxide,
CO(NH
2
)
2
(g) +2NO(g) +1/2O
2
(g)
2N
2
(g) + CO
2
(g) + 2H
2
O(g).
Calculate the ideal-gas heat of reaction
at 77F (Btu/lb mole urea).
V. Applications of Energy
Balances (cont.)
Example V.B(5)
Orimulsion is a tar-like bitumen that uses an
emulsifying agent to produce a liquid. This blend
(15wt% emulsifying agent) can be substituted for oil
in utility burners. Data on orimulsion (exclusive of
emulsifying agent): heating value 16,800 Btu/lb (dry
and ash-free) content (%wt): ash 12.1%, moisture
10.9%, organic 77.0%
The emulsifying agent has no heating value.
Calculate the value (Btu/lb) of the as-delivered
emulsifying fuel.
V. Applications of Energy
Balances (cont.)
Example V.B(6)
A combustor currently operates on high-sulfur waste
coal (gob coal). To reduce sulfur emissions, some
pelletized waste is used to displace 10% by weight
of the gob coal. The heating values of pelletized
waste and gob coal are 6,550 Btu/lb and 5,500
Btu/lb, respectively.
Calculate the ratio of pounds of pellets fired to
pounds of gob coal fired to maintain the same heat
output.
V. Applications of Energy
Balances (cont.)
Example V.B(7)
A boiler is fired with a gas (MW = 16.36) that has the
following composition by volume: methane 97%,
nitrogen 3%. The boiler is designed for a volumetric
fuel rate of 60,000 standard cubic feet (scf) per hour
(60F and 1 atmosphere). Methane has a gross
heat of combustion (HHV) of 1,013 Btu/scf and a net
heat of combustion (LHV) of 913 Btu/scf.
Calculate the firing rate (Btu/hr) to the boiler (with
water as a vapor in the flue gas and 0% excess air).
V. Applications of Energy
Balances (cont.)
Example V.B(8)
An incinerator is designed to process
600 tons/day of municipal solid waste
(MSW). The heating value of the MSW
is 1,100 Btu/lb. The incinerator is
currently being operated at 75% of
capacity with an efficiency of 50%.
Calculate the heat liberated (10
9
Btu/day) by the incinerator.
V. Applications of Energy
Balances (cont.)
C. Applications of Energy Balances in
Processes that Include Reactions
The adiabatic reaction (theoretical flame,
combustion) temperature is defined as the
temperature obtained when
the process is adiabatic and
the limiting reactants react completely.
V. Applications of Energy
Balances (cont.)
Example V.C(1)
Calculate the theoretical flame
temperature for CO gas burned at
constant pressure with 100% excess air,
when the reactants enter at 100C and 1
atm.
V. Applications of Energy
Balances (cont.)
Example V.C(2)
Propylene glycol is produced by the hydrolysis of
propylene oxide (PO) in the liquid phase: CH
3
CHOCH
2
+
H
2
O CH
3
CHOHCH
2
OH
This exothermic reaction occurs readily at room
temperature when catalyzed by sulfuric acid. The feed is
a stream of 24,000 kg/hr with a composition of 10 wt%
propylene oxide, 1 wt % sulfuric acid, 89 wt% water.
Calculate the reactor exit temperature if an adiabatic
reactor is used to achieve a fractional conversion of 0.8
for PO with a feed temperature of 20C.
VI. Volumetric Properties of
Pure Fluids
The quantities of Q and W necessary to
carry out industrial processes are
calculated from thermodynamics
properties.
These properties, such as U, H, and S,
are often evaluated from molar volumes,
V = fn(T, P), yielding equations of state.
VI. Volumetric Properties of
Pure Fluids (cont.)
A. PVT Behavior of Pure Substances
solid
vapor
liquid
1
2
3
Fluid region
Gas region
Pressure
Temperature
Triple point
C
Figure VI.A(1) PT diagram for a pure substance
VI. Volumetric Properties of
Pure Fluids (cont.)
Pressure
Volume
S L
Liquid/vapor
C
Gas
Vapor
Fluid
T
c
Solid/vapor
Figure VI.A(2) PV diagram for a pure substance
VI. Volumetric Properties of
Pure Fluids (cont.)
Figure VI.A(3) TS diagram for a pure substance
T
S
S L
Liquid/vapor
C
Gas
Vapor
Fluid
Solid/vapor
P = const
VI. Volumetric Properties of
Pure Fluids (cont.)
Quality (x)

D = D
f
+ xD
fg
mixture of amount total
vapor of amount
x =
f g
f
D D
D D
x

=
VI. Volumetric Properties of
Pure Fluids (cont.)
Refer to Table VI.A(1) Equipments
energy balances
VI. Volumetric Properties of
Pure Fluids (cont.)
Example VI.A(1)
A stream consisting of saturated steam at 356F with a
bulk velocity of 130 ft/sec and a flow rate of 250 lbm/hr
goes through a boiler that adds heat to the stream at the
rate of 300 Btu/lbm. The superheated steam
subsequently expands through a back-pressure turbine
where it develops 60 hp of shaft work and exits through a
diffuser with a velocity of 1 ft/sec. The elevation change
between the inlet and the outlet of the system is 220 ft.
Assume negligible pressure drop due to friction.
Calculate the quality of the steam at the outlet of the
diffuser.
VI. Volumetric Properties of
Pure Fluids (cont.)
Example VI.A(2)
Spent steam from a turbine is cooled in a
heat exchanger.
When 5,000 lbm/min of steam enters the
heat exchanger, 2,000,000 Btu/min of
heat is removed. Calculate the quality
(% vapor) of the steam exiting the heat
exchanger.
VI. Volumetric Properties of
Pure Fluids (cont.)
B. Single Phase Region
For regions of the diagram where a single
phase exists a correlation connecting P, V,
and T, expressed analytically as fn(P, V, T) is
known as a PVT equation of state.
The ideal gas equation
PV = RT
For real gases, Z is the compressibility factor

Z
RT
PV
=
VI. Volumetric Properties of
Pure Fluids (cont.)
Example VI.B(1)
Dry air and vinyl chloride (C
2
H
3
Cl) are mixed to
produce a saturated mixture at 3739 mm Hg
and 20C. At this temperature, the vapor
pressure of vinyl chloride is 2580 mm Hg. The
average molecular weights of vinyl chloride
and dry air are 62.50 g/mol and 28.96 g/mol,
respectively. Assume the ideal gas law
applies. Calculate the mass of vinyl chloride in
100 cm
3
of saturated mixture.
VII. Ideal Process, Efficiency,
and Cycles
Energy is conserved but how is this
energy converted from one form to
another and how efficiently is this done?
Ideal vs actual processes
Reversible vs irreversible processes
Cycle number of processes applied to
a substance that leaves it in its original
state.
VII. Ideal Process, Efficiency,
and Cycles (cont.)
Efficiencies definitions - refer to your
notes, Table VII(2) Efficiencies
definitions
VII. Ideal Process, Efficiency,
and Cycles (cont.)
Carnot cycle
T
S
1
4
2
3
Figure VI(1) Carnot cycle
Q
in
Q
out
VII. Ideal Process, Efficiency,
and Cycles (cont.)
Rankine cycle
T
S
1
4
2
3
Figure VI(2) Rankine cycle
P
const
VII. Ideal Process, Efficiency,
and Cycles (cont.)
Efficiency relationships - refer to your
notes, Table VI(2) Important work and
efficiency relationships.
VII. Ideal Process, Efficiency,
and Cycles (cont.)
Equipment processes refer to your
notes, Figure VI(3) Adiabatic expansion
process in a turbine or expander and
Figure VI(4) Adiabatic compression
process.
VII. Ideal Process, Efficiency,
and Cycles (cont.)
Example VI(1)
A steam power plant operates on a reheat Rankine cycle
at a mass flow rate of 1 kg/s. The steam enters the high-
pressure turbine at 12 MPa and 612C and is condensed
at a pressure of 12 kPa. The saturated liquid is then
pumped to the boiler. The temperature of the fluid at
state 5 is the same as the temperature at state 3. The
moisture content in the low-pressure turbine is not to
exceed 8%. Assume all devices operate with 100%
efficiency. Calculate the thermal efficiency of the
Rankine cycle operating at these conditions.
VII. Ideal Process, Efficiency,
and Cycles (cont.)
Example VI(2)
The compressor of a simple-cycle gas turbine operates
with an efficiency of 87% while the turbine operates with
an efficiency of 90%. The compressor pressure ratio is 5
and the pressure drop in the combustion chamber is 6%.
The turbine inlet temperature is 1500F. Air enters the
compressor at 70F and 1 atm. The air has an isentropic
exponent of 1.40 and a constant heat capacity of 0.24
Btu/lbm-R. The combustion gas has a heat capacity of
0.2744 Btu/lbm-R and an isentropic exponent of 1.333.
Calculate the thermal efficiency of this simple-cycle gas
turbine.
VII. Ideal Process, Efficiency,
and Cycles (cont.)
Example VI(3)
An ideal gas flowing at a rate of 15 mol/s, a temperature
of 298 K, and at 120 kPa is to be compressed to 1600
kPa using a three-stage isentropic compressor. The
compressor system has an efficiency of 90% and is
driven by an electric motor with 70% efficiency. The
compression ratio is equal for each stage. Assume a
constant outlet temperature of 298 K for the intercoolers.
Calculate the compression power required by the three-
stage compressor.
VIII. Gibbs Energy, Equilibrium
Constant, and Solution
Thermodynamics
A. Gibbs Energy (G)
G is the maximum amount of non-expansion
(without increasing the total volume) work
which can be extracted from a closed
(isothermal, isobaric) system, and this
maximum can be attained only in a
completely reversible process.
A reaction is the result of a system trying to
minimize its Gibbs energy.
VIII. Gibbs Energy, Equilibrium
Constant, and Solution
Thermodynamics
Gibbs energy is defined as
G = H - TS

o
rxn
o
rxn
o
rxn
S

T H

=
o
i f,
reactants
i
i
o
i f,
products
i
i
o
rxn
G

=
VIII. Gibbs Energy, Equilibrium
Constant, and Solution
Thermodynamics (cont.)
Example VIII.A(1)
Liquid methylhydrazine (CH
6
N
2
) reacts
with liquid dinitrogen tetroxide (N
2
O
4
) to
give gaseous carbon dioxide (CO
2
),
gaseous water (H
2
O), and gaseous
nitrogen (N
2
) at 25C and 1 atm.
Calculate the Gibbs energy for the
reaction at 25C.
VIII. Gibbs Energy, Equilibrium
Constant, and Solution
Thermodynamics (cont.)
B. Equilibrium Constant
The equilibrium constant expresses the
equilibrium of a reaction with the final
concentrations of the products and reactants.
For a typical reaction aA + bB pP + qQ the
general form of the equilibrium constant for
liquids is

[ ] [ ]
[ ] [ ]
b
B
a
A
q
Q
p
p
eq
C C
C C
K =
VIII. Gibbs Energy, Equilibrium
Constant, and Solution
Thermodynamics (cont.)
For gases assuming ideal gases and Daltons
Law of partial pressures

The tendency for a reaction to reach an

equilibrium is driven by the Gibbs energy.
The K can be calculated from
= -RTlnK.
[ ] [ ]
[ ] [ ]
b a q p
Y
b
B
a
A
q
Q
p
p
P
P K
P y P y
P y P y
K
+
= =
G

VIII. Gibbs Energy, Equilibrium

Constant, and Solution
Thermodynamics (cont.)
The change of K with T can be determined by
the vant Hoff equation

where His the change in enthalpy of reaction

(heat of reaction) at equilibrium and it is constant.
|
|

\
|

|
|

\
|

=
2 1 T2
T1
T
1
T
1
R
H

K
K
ln
o
VIII. Gibbs Energy, Equilibrium
Constant, and Solution
Thermodynamics (cont.)
Example VIII.B(1)
One (1) mol of carbon monoxide (CO) reacts
with 3 mol of hydrogen (H
2
) at 100C and 1
atm to give methane (CH
4
) and water (H
2
O).
For the reaction
CO(g) + 3H
2
(g) CH
4
(g) + H
2
O(g),
Calculate the numerical value of the
equilibrium constant for the reaction at 100C.
VIII. Gibbs Energy, Equilibrium
Constant, and Solution
Thermodynamics (cont.)
C. Solution Thermodynamics
The thermodynamics of pure substances is
different to that of mixtures.
At common P and T, the vapor phase can
usually be considered ideal and the vapor-
liquid equilibrium can usually be considered
ideal and the vapor-liquid expression can be
simplified to a modified version of the Lewis-
Randall relationship

P y p x
i
o
i i i
=
VIII. Gibbs Energy, Equilibrium
Constant, and Solution
Thermodynamics (cont.)
In non-ideal liquid problems the pure liquid
phase vapor pressure, p
o
, is usually given in
the form of Antoine equation

It should be noted that the p

o
= fn(T) while =
fn(x).
The usual problem dealing with non-ideal
liquids is to find the composition (x) at another
state.
B/T A lnp
o
+ =
VIII. Gibbs Energy, Equilibrium
Constant, and Solution
Thermodynamics (cont.)
Two types of equations for binary mixtures
are
Van Laar equations
Three Suffix Margules equations
Refer to eqns. 40a, 40b, 41a, 41b of your notes.
Two conditions are usually studied
azeotrope and
infinite dilutions.
Refer to Table VIII.C(1) Summary of activity
coefficients of your notes.
VIII. Gibbs Energy, Equilibrium
Constant, and Solution
Thermodynamics (cont.)
Raoults assumptions are
the vapor phase is an ideal gas, PV = RT, and
the liquid phase is an ideal solution, = 1.
When the liquid phase is considered pure, x = 1, then

When it is necessary to calculate the mole fraction of a

species dissolved in liquid the Henrys law can be
applied

P
p
y
o
i
i
=
P y x
i i
=
i
H
VIII. Gibbs Energy, Equilibrium
Constant, and Solution
Thermodynamics (cont.)
Example VIII.C(1)
Dry air and vinyl chloride (C
2
H
3
Cl) are
combined to produce a saturated mixture at
14.3 lbf/in
2
and 77F. At this temperature, the
vapor pressure of vinyl chloride is 5.77 lbf/in
2
.
The average molecular weight of vinyl chloride
and dry air are 62.50 lbm/lbmol and 28.96
lbm/lbmol, respectively. Assume the ideal gas
law applies. Calculate the mass ratio of vinyl
chloride to dry air in the saturated mixture.
VIII. Gibbs Energy, Equilibrium
Constant, and Solution
Thermodynamics (cont.)
Example VIII.C(2)
A vent stream consisting of acetone, air, and a negligible
amount of moisture flows at 200 ft
3
/min at standard
conditions. The acetone is to be separated from the
remaining vapors by condensation. This process requires
a refrigerated condenser system. The inlet volume
fraction of acetone in the vent stream is 0.385. The
required removal efficiency is 90%. The relationship
between the temperature in degrees Celsius and the
vapor pressure of the acetone in mm Hg is
Calculate the temperature required to achieve the desired
removal efficiency.
C 229.664 T
C 1210.595
7.117 logp
o
o
o
mmHg ac,
+
=
VIII. Gibbs Energy, Equilibrium
Constant, and Solution
Thermodynamics (cont.)
Example VIII.C(3)
A combustion chamber receives a feed that
consists of a gaseous waste containing
benzene 1000 ppm (by volume), chloroform
1000 ppm (by volume), and air at 77F. The
molecular weight of the waste gas is 28.97
lbm/lbmol. At 77F, the volumetric heat of
combustion is 3616 Btu/ft
3
for benzene and
705 Btu/ft
3
for chloroform. Calculate the heat
of combustion of the waste gas stream.
VIII. Gibbs Energy, Equilibrium
Constant, and Solution
Thermodynamics (cont.)
Example VIII.C(4)
The Henrys law constant for carbon
dioxide in seawater at 25C is 35.4
atm/(mol/kg). This constant is based on
concentration (c) rather than activity in
the liquid phase.
Calculate the equilibrium concentration
(mol/kg) of CO
2
(aq) with CO
2
partial
pressure at 0.000354 atm.
VIII. Gibbs Energy, Equilibrium
Constant, and Solution
Thermodynamics (cont.)
Example VIII.C(5)
Water (60 lb moles), benzene (20 lb moles), and
toluene (20 lb moles) equilibrate as a liquid mixture
at a pressure of 0.9 atm. The water (W) and the
organics are immiscible, and the benzene (B) and
the toluene (T) form an ideal mixture.
Calculate the saturation pressure (atm) of water, ,
at the bubble-point temperature and the specified
system pressure.
o
W
P
VIII. Gibbs Energy, Equilibrium
Constant, and Solution
Thermodynamics (cont.)
D. Heat Effects of Mixing Processes
For ideal solutions

Heat of solution ( ) heat effect due to

solids or gases dissolved in liquids
Heat of mixing heat effect due to the mixing
of liquid-liquid.
Pi
n
1 i
i avg P
C x C

=
=
solution
H

VIII. Gibbs Energy, Equilibrium

Constant, and Solution
Thermodynamics (cont.)
For any solution

where is the integral heat of formation of

solution at standard conditions per mole of solute,
. is the heat of formation of the solution
itself per mole of solute, and is the heat
of formation of the solute.
is not included.
o
solution
o
solute f,
o
solution f,
H

+ =
o
solution f,
H

o
solution
H

o
solute f,
H

o
O H f,
2
H

VIII. Gibbs Energy, Equilibrium

Constant, and Solution
Thermodynamics (cont.)
Example VIII.D(1)
Calculate the heat of formation of LiCl in
12 mol of H
2
O at 25C.
VIII. Gibbs Energy, Equilibrium
Constant, and Solution
Thermodynamics (cont.)
Example VIII.D(3)
Two pure process streams are fed to a perfectly mixed
tank kept at 77F. One stream consists of pure
compound M. The other stream is water (H
2
O). The
solution in the tank is produced at a flow rate of 28,800
lbm/hr of a 15% (by weight) solution. The molecular
weight component M is 42.39 lbm/lbmol and that of H
2
O
is 18.015 lbm/lbmol. In the evaporator, 18,000 lbm/hr of
H
2
O are removed. Calculate the rate of the heat produced
in the tank.
The End
Study hard and go for it